Silicone grafted thermoplastic elastomeric copolymers and hair and skin care compositions containing the same

ABSTRACT

The present invention relates to water or alcohol soluble or dispersible silicone grafted thermoplastic elastomeric copolymers and to cosmetic and pharmaceutical compositions containing these copolymers. This invention especially relates to copolymers useful for hair styling purposes, and to hair styling compositions containing these copolymers. This invention further relates to copolymers useful for providing cosmetic and pharmaceutical compositions for topical application to the skin. These topical skin care compositions are useful for delivering and/or transdermally transporting active ingredients to or thorugh the skin.

This is a continuation of application Ser. No. 08/748,705, now U.S. Pat.No. 5,916,547, filed on Nov. 13, 1996, which is a divisional ofapplication Ser. No. 08/446,189, filed on May 19, 1995, now abandoned,which is a continuation of application Ser. No. 08/257,961, filed onJun. 16, 1994, now abandoned, which is a continuation-in-part ofapplication Ser. No. 08/236,881, filed on Apr. 29, 1994, now abandoned,which is a continuation of Ser. No. 08/110,592, filed on Aug. 23, 1993now abandoned.

TECHNICAL FIELD

The present invention relates to water or alcohol soluble or dispersiblesilicone grafted thermoplastic elastomeric copolymers and to cosmeticand pharmaceutical compositions containing these copolymers. Thesecopolymers are useful for hair setting and styling purposes. Aparticularly useful application for these copolymers is in hair sprayand mousse compositions. This invention further relates to copolymersuseful for incorporating into cosmetic and pharmaceutical compositionsfor topical application to the skin. Skin care compositions containingthese copolymers are useful for delivering and/or transdermallytransporting a wide variety of active ingredients to and/or through theskin.

BACKGROUND OF THE INVENTION

In the hair care area, the desire to have hair retain a particular styleor shape is widely held. Such style retention is generally accomplishedby either of two routes: permanent chemical alteration of the hair fiberor temporary alteration of hair style or shape. A temporary alterationis one which can be removed by water or by shampooing. Temporary stylealteration has generally been accomplished by application of acomposition to dampened hair after shampooing and/or conditioning andprior to drying and/or styling. Products in the form of mousses, gels,lotions, or sprays are most commonly used for this purpose. Once thedesired style is achieved, spray products are commonly used to helpretain the style. These various hair care products utilize a variety ofgums and resins for providing styling and retention. However, the gumsand resins currently used tend to feel either too sticky or too stiffupon the hair. Also, these gums and resins do not wash out as easily asdesired. Therefore, the need exists for improved styling and styleretention materials which provide a strong, lasting, hold without beingeither too stiff or too sticky, and yet which are easily removed byshampooing. Furthermore, because most hair care styling compositions arewater and/or alcohol based, it is necessary that these materials havegood solubility or dispersibility in these bases.

Thermoplastic elastomeric copolymers are well known. These copolymerscombine thermoplastic properties, which give them solubility andstrength, with rubber-like elastic properties, which give themflexibility and shape retention. However, despite these highly desirableproperties, most thermoplastic elastomeric copolymers are generallyinsoluble or poorly soluble in water and/or alcohol systems and wouldnot be suitable in hair care compositions. Therefore, thermoplasticelastomeric copolymers having good water and/or alcohol solubility wouldbe useful for developing improved hair care compositions.

It is also known that polymers can be modified by the incorporation orgrafting of silicon. Silicon grafted polymers tend to have a low surfaceenergy and provide unique aesthetic and formulation advantages notusually obtained from non-silicon grafted polymers. However, silicongrafted thermoplastic elastomeric copolymers are heretofore unknown.

In the present invention new classes of thermoplastic elastomericcopolymers have been developed which have the desired flexibility,strength, and elastic properties and yet are readily soluble and/ordispersible in water and/or alcohol systems. These copolymers alsoincorporate polysiloxane side chains which further modify their surfaceproperties to give them a smooth, slick feel, and make them easier toformulate into a wide variety of vehicles. Furthermore, these materialsprovide hair care compositions which leave the hair feeling natural,i.e. not very stiff or sticky.

In addition to the hair care benefits provided by silicon containingthermoplastic elastomeric copolymers, it has been found that thesematerials are also useful for incorporation into a wide variety ofcosmetic and pharmaceutical compositions for topical application to theskin. These copolymers provide topical compositions which are moreeasily and uniformly spread upon the skin, which feel good upon theskin, and yet which are highly substantive. Furthermore, thesecopolymers are useful for enhancing the penetration of a wide variety ofcosmetic and pharmaceutical actives into the skin, or alternatively,through the skin for systemic delivery.

It is an object of the present invention to provide novel, water and/oralcohol soluble and/or dispersible silicone grafted thermoplasticelastomeric copolymers.

It is another object of the present invention to provide novel siliconegrafted thermoplastic elastomeric copolymers useful in hair carecompositions.

It is another object of the present invention to provide novel hair carecompositions having improved styling and/or hold properties and havingimproved aesthetics.

It is another object of the present invention to provide novel siliconegrafted thermoplastic elastomeric copolymers useful in topical skin carecosmetic and pharmaceutical compositions.

It is another object of the present invention to provide novel topicalcosmetic and pharmaceutical compositions useful for delivering a widevariety of cosmetic materials and pharmaceutical actives to and/orthrough the skin.

These and other objects will become readily apparent from the detaileddescription which follows.

SUMMARY OF THE INVENTION

The present invention relates to a water or alcohol soluble ordispersible thermoplastic elastomeric copolymer having a backbone andtwo or more hydrophilic polymeric side chains and one or morepolysiloxane side chains, said copolymer formed from thecopolymerization of randomly repeating A, B, and C units wherein saidcopolymer comprises:

(i) from about 20% to about 89.9% by weight of said A units, whereinsaid A units are monomer units copolymerizable with said B and C units;

(ii) from about 10% to about 60% by weight of said B units, wherein saidB units are hydrophilic macromonomer units having a polymeric portionand a moiety copolymerizable with said A and C units; and

(iii) from about 0.1 to about 20% by weight of said C units, whereinsaid C units are polysiloxane macromonomer units having a polymericportion and a moiety copolymerizable with said A and B units,

wherein said A units, in conjunction with said copolymeriable moietiesof said B units and said C units, forms said backbone; wherein saidpolymeric portion of said B units forms said hydrophilic side chains;wherein said polymeric portion of said C units forms said polysiloxaneside chains; wherein said copolymer has a weight average molecularweight greater than about 10,000, and wherein said copolymer exhibits atleast two distinct T_(g) values, said first T_(g) corresponding to saidbackbone and having a value less than about 0° C., and said second T_(g)corresponding to said hydrophilic polymeric side chains and having avalue greater than about 25° C.

The present invention also relates to a water or alcohol soluble ordispersible thermoplastic elastomeric copolymer having a backbone andtwo or more hydrophilic polymeric side chains and one or morepolysiloxane side chains, said copolymer formed from thecopolymerization of randomly repeating A, B, and C units andcorresponding to the formula

[A]_(a)[B]_(b)[C]_(c)

wherein A is at least one polymerizable monomer; preferably a monomerunit corresponding to the formula

wherein X is selected from the group consisting of —OH, —OM, —OR⁴, —NH₂,—NHR⁴, and —N(R⁴)₂; M is a cation selected from the group consisting ofNa+, K+, Mg++, Ca++, Zn++, NH₄+, alkylammonium, dialkylammonium,trialkylammonium, and tetralkylammonium; each R⁴ is independentlyselected from the group consisting of H, C₁-C₈ straight or branchedchain alkyl, N,N-dimethylaminoethyl, methyl quaternizedN,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and2-ethoxyethyl; and R⁵ and R⁶ are independently selected from the groupconsisting of H, C₁-C₈ straight or branched chain alkyl, methoxy,ethoxy, 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl; and a is aninteger of about 100 or greater.

B is at least one hydrophilic macromonmer unit copolymerizable with Aand C corresponding to the formula

wherein E is an ethylenically unsaturated moiety, copolymerizable with Aand C, selected from the group consisting of vinyl, allyl, acryloyl,methacryloyl, ethacryloyl, 3-vinylbenzoyl, and 4-vinylbenzoyl; R and R′are independently selected from the group consisting of H and C₁-C₈straight or branched chain alkyl; m is an integer from about 10 to about2000; and b is an integer of about 2 or greater.

C is at least one polysiloxane macromonomer unit copolymerizable with Aand B corresponding to the formula

E′(Y)_(n)Si(R⁷)_(3-t)(Z)_(t)

wherein E′ is an ethylenically unsaturated moiety copolymerizble with Aand B; Y is a divalent linking group; R⁷ is selected from the groupconsisting of H, lower alkyl, aryl, or alkoxy; Z is a monovalentsiloxane polymeric moiety having a number average molecular weight of atleast about 500, is essentially unreactive under copolymerizationconditions, and is pendant from said backbone after polymerization; n is0 or 1; t is an integer from 1 to 3; and c is an integer of about 1 orgreater.

In further embodiments, B is at least one hydrophilic macromonomer unitcopolymerizable with A and C corresponding to the formula

wherein R and R′ are independently selected from the group consisting ofH and C₁-C₈ straight or branched chain alkyl; and m is an integer fromabout 10 to about 2000.

In further embodiments, B is at least one hydrophilic macromonmer unitcopolymerizable with A and C corresponding to the formula

wherein E is an ethylenically unsaturated moiety, copolymerizable with Aand C, selected from the group consisting of vinyl, allyl, acryloyl,methacryloyl, ethacryloyl, 3-vinylbenzoyl, and 4-vinylbenzoyl, andmixtures thereof; R″ is selected from the group consisting of hydrogenand C₁-C₄₀ straight or branched chain alkyl; R³ is selected from thegroup consisting of H, and C₁-C₈ straight or branched chain alkyl; and mis an integer from about 20 to about 2000.

In further embodiments, the present invention relates to hair carecompositions, especially hair setting and styling compositions,containing these copolymers.

In further embodiments, the present invention relates to cosmetic andpharmaceutical compositions containing these copolymers for topicalapplication to the skin for the delivery of cosmetic materials andpharmaceutical actives onto, into and/or through the skin.

All percentages and ratios used herein are by weight of the totalcomposition and all measurements made are at 25° C., unless otherwisedesignated. The invention hereof can comprise, consist of, or consistessentially of, the essential as well as optional ingredients andcomponents described herein.

DETAILED DESCRIPTION OF THE INVENTION

The term “thermoplastic elastomeric copolymer” as used herein means thatthe copolymer has both thermoplastic and elastomeric properties. Theterm “thermoplastic elastomeric copolymer” is one familiar to those ofordinary skill in polymer science. By “thermoplastic” is meant that uponheating, the copolymer softens and upon cooling it rehardens; upon beingsubject to stress it begins to flow and upon removal of stress it stopsflowing. By “elastomeric” is meant that the copolymer has an elasticmodulus such that the copolymer exhibits a resistance to deformation andhas limited extensibility and retraction. In other words, the copolymertends to recover its size and shape after deformation.

“Grafted copolymers” is a term familiar to those of ordinary skill inpolymer science and is used to describe copolymers onto which anotherchemical moiety has been added or “grafted”. The term “silicone grafted”as used herein means that these copolymers contain pendant polysiloxaneside chains, or in other words, these polymers can be formed from the“grafting” or incorporation of polysiloxane side chains onto or into thecopolymer.

The term “macromonomer” is one familiar to those of ordinary skill inpolymer science, and is used to describe a polymeric material containinga polymerizable moiety. In other words, a macromonomer is amacromolecular monomer, which is essentially a high molecular weighttype of monomer building block unit which can be used in apolymerization reaction to form polymers with itself, with othermonomers, or with other macromonomers.

The term “water or alcohol soluble or dispersible” as used herein meansthat these copolymers are either freely soluble in or dispersible (as astable suspension) in at least one of the following solvents, oralternatively, in any combination of one of the following solvents:water, methanol, ethanol, and isopropanol. By “soluble” is meant thatthe copolymer is soluble in the solvent or solvents at 25° C. at aconcentration of at least about 20 mg/mL, more preferably about 50mg/mL, and most preferably about 100 mg/mL. By “dispersible” is meantthat the copolymer forms a stable, uniform suspension (without theaddition of further materials such as emulsifiers) when combined withthe solvent or solvents at 25° C. at a concentration of at least about20 mg/mL, more preferably about 50 mg/mL, and most preferably about 100mg/mL.

Silicone Grafted Thermoplastic Elastomeric Copolymers

The copolymers of the present invention are characterized in having anelastomeric or flexible backbone; at least two thermoplastic,hydrophilic side chains; and at least one polysiloxane chain. Thiscombination of elastomeric, thermoplastic, and polysiloxane moieties ina single copolymer provides the unique and useful properties of thesematerials. The copolymers of the present invention, can also be referredto as “graft copolymers” because they can be prepared from thecopolymerization of monomer units and macromonmer and polysiloxaneunits. In other words, the macromonomer and polysiloxane units are“grafted” or incorporated into the copolymer.

These copolymers exhibit at least two distinct immiscible phases.Without being limited by theory, it is believed that the hydrophilicside chains of these copolymers are closely associated with each otherthereby existing in one phase, while the backbone of the copolymerremains in a separate phase. Depending on the relative percentage ofpolysiloxane moieties in the copolymers, the polysiloxane side chainscan also form yet another distinct phase. A consequence of this phaseimmiscibility is that these copolymers exhibit at least two distinctglass transition temperatures or, “T_(g)'s”, namely one T_(g) for thebackbone and one T_(g) for the hydrophylic side chains. The copolymerscan also exhibit a third glass transition temperature corresponding tothe polysiloxane side chains. Whether such a third T_(g) is observablewill depend upon a number of factors including the percent silicon inthe copolymer, the number of polysiloxane side chains in the copolymer,the temperature separation between each of the T_(g)'s involved, andother such physical factors.

T_(g) is a well known term of art in polymer science used to describethe temperature at which a polymer or portion thereof undergoes atransition from a solid or brittle material to a liquid or rubber-likematerial. Glass transition temperatures can be measured using standardtechniques that are well known to the polymer scientist of ordinaryskill in the art. One particularly useful technique for determiningglass transitions is differential scanning calorimetry (also known asDSC). The glass transition phenomenon in polymers is described inIntroduction to Polymer Science and Technology: An SPE Textbook, (eds.H. S. Kaufman and J. J. Falcetta), (John wiley & Sons: 1977), which isincorporated by reference herein in its entirety.

The T_(g) of the backbone of the copolymers herein (i.e. that part ofthe copolymer not containing the hydrophilic side chains and thepolysiloxane side chains) should be less than about 0° C. Preferably theT_(g) of the backbone should be from about −10° C. to about −130° C.,more preferably from about −20° C. to about −125° C., and mostpreferably from about −45° C. to about −120° C. The T_(g) of thehydrophilic side chain of the copolymers (i.e. that part of thecopolymer not containing the backbone and polysiloxane side chains) isgreater than about 20° C. Preferably the T_(g) of the hydrophilicsidechain should be from about 25° C. to about 200° C., more preferablyfrom about 30° C. to about 175° C., and most preferably from about 35°C. to about 150° C. The T_(g) of the polysiloxane side chains of thecopolymers (i.e. that part of the copolymer not containing the backboneand hydrophilic side chains) is approximately about −120° C. Asdescribed above, a distinct T_(g) is not always observable for thepolysiloxane side chains of these copolymers.

Because these copolymers possess at least two distinct T_(g)'s, for thebackbone and the hydrophilic side chains, these copolymers are useful inhair styling and setting compositions. Without being limited by theory,it is believed that when these copolymers are subjected to temperaturesabove these T_(g)'s, they are capable of flowing and can provide greatflexibility during the styling process (e.g., when curling irons, blowdriers, and other heat sources are applied to the hair). Upon cooling ofthe copolymer to room temperature, the copolymer is typically below theT_(g) of the hydrophilic side chains, and the copolymer possessesstructural rigidity from these hydrophilic side chains, and yet hasflexibility from the backbones and polysiloxane side chains, and canprovide a strong, yet flexible, hair hold or style retention.Additionally, the siloxane side chains of these copolymers provide asmooth silky, feel and shine to the hair.

Furthermore, at skin temperatures, these copolymers would be at atemperature which is essentially below the T_(g) of the hydrophilic sidechains. These copolymers can enhance the film forming properties of skincare compositions, and provide benefits such as better and more evendistribution upon the skin.

The copolymers of the present invention are formed from thecopolymerization of randomly repeating A, B, and C units, preferablywherein the A units are selected from at least one polymerizable,ethylenically unsaturated monomer unit; the B units are selected from atleast one hydrophilic macromonomer unit which contains a polymericportion and a copolymerizable moiety, preferably an ethylenicallyunsaturated moiety which is copolymerizable with the A and C units; andthe C units are selected from at least one polysiloxane macromonomerunit which contains a polymeric portion and a copolymerizbale moiety,preferably an ethylenically unsaturated moiety which is copolymerizablewith the A and B units. In preferred embodiments of these copolymers,the backbone is formed from the polymerization of the A monomer unitswith the ethylenically unsaturated portion of the hydrophilic Bmacromonomer unit, and the ethylenically unsaturated portion of thepolysiloxane C macromonomer unit. The polymeric portion of the Bmacromonomer units forms the hydrophilic side chains of the copolymer.The polymeric portion of the C macromonomer units forms the polysiloxaneside chains of the copolymer. The A, B, and C units can be selected froma wide variety of structures as long as the limitations of the copolymerare met (e.g., solubility, T_(g)'s, and molecular weights).

The A monomer units of the copolymers of the present invention cancomprise from about 20% to about 89.9%, more preferably from about 35%to about 85%, and most preferably from about 50% to about 80%, byweight, of the copolymers.

The hydrophilic B macromonomer units can comprise from about 10% toabout 60%, more preferably from about 20% to about 55%, and mostpreferably from about 30% to about 50%, by weight of the copolymers.

The C polysiloxane macromonomer units can comprise from about 0.1% toabout 20%, more preferably from about 1% to about 15%, and mostpreferably from about 2% to about 10%, by weight of the copolymers.

The copolymers of the present invention have a weight average molecularweight of at least about 10,000. There is no upper limit for molecularweight except that which limits applicability of the invention forpractical reasons, such as viscosity, processing, aestheticcharacteristics, formulation compatibility, etc. The weight averagemolecular weight is less than about 5,000,000, more generally less thanabout 2,500,000, and typically less than about 1,500,000. Preferably,the weight average molecular weight is from about 10,000 to about5,000,000, more preferably from about 75,000 to about 1,000,000, evenmore preferably from about 100,000 to about 850,000, and most preferablyfrom about 125,000 to about 750,000.

Alternatively, the copolymers of the present invention can also berepresented by the formula

[A]_(a)[B]_(b)[C]_(c)

wherein A, B, and C are as described herein; and where a is an integerof about 100 or greater, preferably a is an integer from about 100 toabout 3000, more preferably from about 250 to about 2000, and mostpreferably from about 350 to about 1500; b is an integer of about 2 orgreater, preferably from about 2 to about 50, more preferably from about2 to about 20, and most preferably from about 2 to about 10; and c is aninteger of about 1 or greater, preferably from about 1 to about 25, morepreferably from about 1 to about 10, and most preferably from about 1 toabout 5. In this formula, it is expressly intended that even thoughranges are provided for the subscripts a, b, and c, these subscripts arenot intended to strictly limit the polymers herein so long as thephysical properties, e.g., T_(g), solubility, and the like, of thepolymers are achieved. When the copolymers herein are described by theformula disclosed in this paragraph it has been found useful to describethe copolymers by their number average molecule weights. The numberaverage molecular weight is less than about 2,500,000, more generallyless than about 1,500,000, and typically less than about 1,000,000.Preferably, the number average molecular weight is from about 15,000 toabout 1,000,000, more preferably from about 20,000 to about 500,000, andmost preferably from about 25,000 to about 250,000.

By appropriate selection and combination of the particular A, B, and Cunits and by the choice of specific relative ratios of the units wellwithin the ability of one of ordinary skill in the art, the copolymerscan be optimized for various physical properties such as solubility,T_(g)'s, and the like, and for compatibility with other ingredientscommonly used in hair care and skin care applications.

When the copolymers of the present invention are incorporated into hairand/or skin care compositions, the copolymers typically comprise fromabout 0.1% to about 25%, preferably from about 0.5% to about 20%, morepreferably from about 1% to about 10%, and most preferably from about 2%to about 5% of the composition, although higher or lower amounts can beused depending upon the particular application.

Monomer “A” Units

The “A” monomer unit is selected from polymerizable monomers, preferablyethylenically unsaturated monomers. Either a single A monomer orcombinations of two or more A monomers can be utilized. The A monomersare selected to meet the requirements of the copolymer. By“polymerizable”, as used herein, is meant monomers that can bepolymerized using any conventional synthetic techniques. Monomers thatare polymerizable using conventional free radical initiated techniquesare preferred. The term “ethylenically unsaturated” is used herein tomean monomers that contain at least one polymerizable carbon-carbondouble bond (which can be mono-, di-, tri-, or tetra-substituted).

The A monomer units of the copolymers of the present invention cancomprise from about 20% to about 89.9%, more preferably from about 35%to about 85%, and most preferably from about 50% to about 80%, byweight, of the copolymers.

The ethylenically unsaturated A monomer units preferably can bedescribed by the following formula

wherein X is selected from the group consisting of —OH, —OM, —OR⁴, —NH₂,—NHR⁴, and —N(R⁴)₂; M is a cation selected from the group consisting ofHa+, K+, Mg++, Ca++, Zn++, NH₄+, alkylammonium, dialkylammonium,trialkylammonium, and tetralkylammonium; each R⁴ is independentlyselected from the group consisting of H, C₁-C₈ straight or branchedchain alkyl, N,N-dimethylaminoethyl, methyl quaternizedN,N-dimethylaminoethyl, 2-hydroxyethyl, 2-methoxyethyl, and2-ethoxyethyl; and R⁵ and R⁶ are independently selected from the groupconsisting of H, C₁-C₈ straight or branched chain alkyl, methoxy,ethoxy, 2-hydroxyethoxy, 2-methoxyethyl, and 2-ethoxyethyl.

Representative nonlimiting examples of monomers useful herein includeacrylic acid and salts, esters, and amides thereof. The salts can bederived from any of the common nontoxic metal, ammonium, or substitutedammonium counter ions. The esters can be derived from C₁₋₄₀ straightchain, C3-40 branched chain, or C3-40 carbocyclic alcohols; frompolyhydric alcohols having from about 2 to about 8 carbon atoms and fromabout 2 to about 8 hydroxy groups (nonlimiting examples of which includeethylene glycol, propylene glycol, butylene glycol, hexylene glycol,glycerin, and 1,2,6-hexanetriol); from amino alcohols (nonlimitingexamples of which include aminoethanol, dimethylaminoethanol, anddiethylaminoethanol, and their quaternized derivatives); or from alcoholethers (nonlimiting examples of which include methoxyethanol, and ethoxyethanol). The amides can be unsubstituted, N-alkyl or N-alkylaminomono-substituted, or N,N-dialkyl or N,N-dialkylamino di-substituted,wherein the alkyl or alkylamino group can be derived from C₁₋₄₀ straightchain, C3-40 branched chain, or C3-40 carbocylic moieties. Additionally,the alkylamino groups can be quaternized. Also useful as monomers aresubstituted acrylic acids and salts, esters, and amides thereof [whereinthe substituents are on the two and three carbon positions of theacrylic acid and are independently selected from the group consisting ofC₁₋₄ alkyl, —CN, —COOH (e.g., methacrylic acid, ethacrylic acid, and3-cyano acrylic acid)]. The salts, esters, and amides of thesesubstituted acrylic acids can be defined as described above for theacrylic acid salts, esters, and amides. Other useful monomers includevinyl and allyl esters of C₁₋₄₀ straight chain, C3-40 branched chain, orC3-40 carbocylic carboxylic acids; vinyl and allyl halides (e.g., vinylchloride and allyl chloride); vinyl and allyl substituted heterocyliccompounds (e.g., vinyl pyrridine and allyl pyridine); vinylidenechloride; and hydrocarbons having at least one carbon-carbon double bond(e.g., styrene, alpha-methylstyrene, t-butylstyrene, butadiene,isoprene, cyclohexadiene, ethylene, propylene, 1-butene, 2-butene,isobutylene, vinyl toluene); and mixtures thereof.

Preferred A monomers useful herein include those selected from the groupconsisting of acrylic acid, methacrylic acid, ethacrylic acid, methylacrylate, ethyl acrylate, n-butyl acrylate, iso-butyl acrylate, t-butylacrylate, 2-ethylhexyl acrylate, decyl acrylate, methyl methacrylate,ethyl methacrylate, n-butyl methacrylate, iso-butyl methacrylate,t-butyl methacrylate, 2-ethylhexyl methacrylate, decyl methacrylate,methyl ethacrylate, ethyl ethacryl ate, n-butyl ethacrylate, iso-butylethacrylate, t-butyl ethacrylate, 2-ethylhexyl ethacrylate, decylethacrylate, 2,3-dihydroxypropyl acrylate, 2,3-dihydroxypropylmethacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate,hydroxypropyl methacrylate, glyceryl monoacrylate, glycerylmonomethacrylate, acrylamide, methacrylamide, ethacrylamide, N-methylacrylamide, N,N-dimethyl acrylamide, N,N-dimethyl methacrylamide,N-ethylacrylamide, N-isopropyl acrylamide, N-butyl acrylamide, N-t-butylacrylamide, N,N-di-n-butylacrylamide, N,N-diethylacrylamide, N-octylacrylamide, N-octadecyl acrylamide, N-phenyl acrylamide, N-methylmethacrylamide, N-ethylmethacrylamide, N-dodecylmethacrylamide,N,N-dimethylaminoethyl acrylamide, quaternized N,N-dimethylaminoethylacrylamide, N,N-dimethylaminoethyl methacrylamide, quaternizedN,N-dimethylaninoethyl methacrylamide, N,N-dimethylaminoethyl acrylate,quaternized N,N-dimethylaminoethyl acrylate, N,N-dimethylaminoethylmethacrylate, quaternized N,N-dimethylaminoethyl acrylate, quaternizedN,N-dimethylaminoethyl methacrylate, 2-hydroxyethyl acrylate,2-hydroxyethyl methacrylate, 2-hydroxyethyl ethacrylate, glycerylacrylate, 2-methoxyethyl acrylate, 2-methoxyethyl methacrylate,2-methoxyethyl ethacrylate, 2-ethoxyethyl acrylate, 2-ethoxyethylmethacrylate, 2-ethoxyethyl ethacrylate, maleic acid, maleic anhydrideand its half esters, crotonic acid, itaconic acid, angelic acid,diallyldimethyl ammonium chloride, vinyl pyrrolidone, methyl vinylether, methyl vinyl ketone, maleimide, vinyl pyridine, vinyl imidazole,vinyl furan, styrene sulfonate, allyl alcohol, vinyl alcohol, vinylcaprolactam, and mixtures thereof.

More preferred A monomers are those selected from the group consistingof methyl acrylate, methyl methacrylate, methyl ethacrylate, ethylacrylate, ethyl methacrylate, ethyl ethacrylate, n-butyl acrylate,n-butyl methacrylate, q-butyl ethacrylate, 2-ethylhexyl acrylate,2-ethylhexyl methacrylate, 2-ethylhexyl ethacrylate, N-octyl acrylamide,2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethylacrylate, quaternized N,N-dimethylaminoethyl acrylate, and mixturesthereof.

Most preferred A monomers are those selected from the group consistingof n-butyl acrylate, 2-ethylhexyl acrylate, N-octyl acrylamide,2-methoxyethyl acrylate, 2-hydroxyethyl acrylate, N,N-dimethylaminoethylacrylate, quaternized N,N-dimethylaminoethyl acrylate and mixturesthereof.

Hydrophilic “B” Macromonomer Units

A macromonomer is a large polymeric type of monomer unit which can befurther polymerized with itself, with other conventional monomers, orwith other macromonomers. The term “macromonomer” is one that isfamiliar to the polymer chemist of ordinary skill in the art.

The hydrophilic “B” macromonomer units of the present invention arelarge polymeric building blocks containing repeating structural units.The B macromonomers can be formed from the polymerization of smallermonomer units. The B macromonomers encompass a wide variety ofstructures and are copolymerizable with the A monomer and the Cpolysiloxane macromonomer units. Either a single B macromonomer orcombinations of two or more B macromonomers can be utilized. In eithercase, the B macromonomers are selected to meet the requirements of thecopolymer.

The hydrophilic B macromonomers comprise from about 10% to about 60%,more preferably from about 20% to about 55%, and most preferably fromabout 30% to about 50%, by weight of the copolymers.

By the term “copolymerizable” as used herein is meant B macromonomersthat can be reacted with the A monomer and C polysiloxane macromonomerin a polymerization reaction using any conventional synthetictechniques. “Copolymerization” is a term of art used to refer to thesimultaneous polymerization of two or more different monomers. In thepresent invention, B macromonomers that are copolymerizable with Amonomers and C polysiloxane macromonomers using conventional freeradical initiated techniques are preferred. By the term “hydrophilic” asused herein is meant B macromonomers that are soluble in or have anaffinity for water and/or other polar, water-soluble solvent materials(e.g., methanol, ethanol, propanol, isopropanol and the like).“Hydrophilic” is also a term of art used to described a substance havinga strong tendency to absorb water which results in the swelling,solubilization, or dispersion of the substance in water. Without beinglimited by theory, the hydrophilic B macromonomer units are believed tocontribute to the overall water or alcohol soluble or dispersibleproperties of the copolymers.

B macromonomers that are useful herein contain a polymeric portion and acopolymerizable moiety, preferably an ethylenically unsaturated moietythat is copolymerizable with the A and C units. The term “ethylenicallyunsaturated” is used herein to mean B macromonomers that contain atleast one carbon-carbon double bond (which can be mono-, di-, tri-, ortetra-substituted). Typically, the preferred B macromonomers are thosethat are endcapped with the ethylenically unsaturated moiety. By“endcapped” as used herein is meant that the ethylenically unsaturatedmoiety is at or near a terminal position of the macromonomer. However,this definition of “endcapped” is not intended to limit the macromonomerto only those macromonomers which terminate in a carbon-carbon doublebond (whether mono-, di-, tri-, or tetra-substituted).

The hydrophilic B macromonomers of the present invention can besynthesized utilizing a variety of standard synthetic proceduresfamiliar to the polymer chemist of ordinary skill in the art.Furthermore, these macromonomers can be synthesized starting fromcommercially available polymers. Typically the weight average molecularweight of the macromonbmer is from about 1000 to about 200,000, morepreferably from 1500 to about 30,000, and most preferably from about2000 to about 25,000.

For example, the hydrophilic B macromonomers can be synthesized by thepolymerization (acid, base, free radical, or auto-initiated) of ahydrophilic monomer to form a polymer which is subsequently reacted withor “endcapped” with a copolymerizable structural unit E, preferably anethylenically unsaturated moiety. Alternatively, the 8 macromonomers canbe synthesized starting with commercially available hydrophilic polymerswhich are “endcapped” with the structural unit E. In yet anotheralternative, the B macromonomer can be synthesized by starting with thestructural unit E, and polymerizing onto it the desired hydrophilicmonomer units. It is to be understood that in this third alternative,the ethylenically unsaturated moiety of the E unit is not consumed inthe synthesis but its integrity is preserved for subsequentcopolymerization of the B macromonomer with the A and C units. All ofthe synthetic alternatives are merely illustrative in that any othersuitable synthetic procedures can be utilized to prepare the Bmacromonomers and copolymers of the present invention.

The B macromonomers can be described by the following formula

[I]_(n)—[W]_(m)—E

W is a hydrophilic monomer unit, and m is an integer from about 10 toabout 2000, preferably from about 15 to about 300, and more preferablyfrom about 20 to about 2S0, so that the macromonomer meets the weightaverage molecular weight requirements set forth above. Preferred is whenW is a hydrophilic monomer unit selected from the group consisting ofoxazolines, N-alkyloxazolines, alkylene glycols, N-vinylpyrrolidones,N-allylpyrrolidones, vinylpyridines, allylpyridiens, vinylcaprolactams,allylcaprolactams, vinylimidazoles, allylimidaoles, vinylfurans,allylfurans, vinyltetrahydrofurans, allyltetrahydrofurans, and mixturesthereof. More preferred is wherein W is a monomer unit selected from thegroup consisting of N-alkyloxazolines, alkylene glycols, and mixturesthereof. Most preferred is wherein W is a monomer unit selected fromN-alkyloxazolines.

E is a copolymerizable moiety or “endcapping” group. Preferably E is anethylenically unsaturated. More preferred is when E is selected from thegroup consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl,styryl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl,1-butenyl, 1-propenyl, isobutenyl, isoprenyl, cyclohexyl, cylcopentyl,and mixtures thereof. Even more preferred is when E is selected from thegroup consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl,3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl,1-propenyl, isobutenyl, and mixtures thereof. Kost preferred is when Eis selected from the group consisting of vinyl, allyl, acryloyl,methacryloyl, ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, and mixturesthereof.

I is an optionally present chemical moiety. In other words, n is aninteger selected from zero and one. Without being limited by theory, Ican be derived from a chemical initiator or solvent used in thesynthesis of the B macromonomer. Nonlimiting examples of such initiatorsfrom which I can be derived include hydrogen ion, hydrogen radical,hydride ion, hydroxide ion, hydroxyl radical, peroxide radical, peroxideanion, C1-20 carbocations, C1-20 carbanions, C1-20 carbon radicals,C1-20 aliphatic and aromatic alkoxy anions, ammonium ion, andsubstituted ammonium ions (e.g., C1-20 alkyl and C1-20 alkoxysubstituted). I can be derived from any useful solvent, nonlimitingexamples of which inicude water, methanol ethanol, propanol,isopropanol, acetone, hexane, dichloromethane, chloroform, benzene, andtoluene. Nonlimiting examples of I include chemical moieties selectedfrom the group consisting of H, C1-C6 alkyl, phenyl, 4-methylphenyl, andbenzyl; preferably H, methyl, ethyl, and phenyl; and more preferably H,methyl, and ethyl.

Representative examples of classes of endcapped B macromonomers usefulherein include those selected from the group consisting of endcappedpoly(N-alkyloxazolines), endcapped polyalkylene glycols, endcappedpolyalkylene glycol monoalkyl ethers, endcappedpoly(N-vinylpyrrolidones), endcapped poly(N-allylpyrrolidones),endcapped polyvinylpyridines, endcapped polyallylpyridines, endcappedpolyvinylcaprolactams, endcapped polyallylcaprolactams, endcappedpolyvinylimidazoles, endcappped polyallylimidazoles, endcappedpolyvinylfurans, endcapped polyvinyltetrahydrofurans, endcappedpolyallylfurans, endcapped polyacrylic acids, endcapped polymethacrylicacids, endcapped polyallyltetrahdyrofurans, and mixtures thereof.

Preferred are macromonomers selected from the group consisting ofendcapped poly(N-alkyloxazolines), endcapped polyalkylene glycols,endcapped polyalkylene glycol monoalkyl ethers, and mixtures thereof.

More preferred are endcapped poly(N-alkyloxazoline) macromonomers.

Examples of endcapped poly(N-alkyloxazoline) macromonomers are thosehaving.the following chemical formula:

wherein R and R′ are independently selected from H or C₁₋₈ straight orbranched chain alkyl, more preferably R and R′ are independentlyselected from H, methyl, or ethyl; and most preferably R is methyl andR′ is ethyl. E is a copolymerizable, ethylenically unsaturated moiety(i.e. the endcapping moiety). Preferred is when E is selected from thegroup consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl,styryl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl,1-butenyl, 1-propenyl, isobutenyl, isoprenyl, cyclohexyl, cylcopentyl,and mixtures thereof. More preferred is when E is selected from thegroup consisting of vinyl, allyl, acryloyl, methacryloyl, ethacryloyl,3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl,1-propenyl, isobutenyl, and mixtures thereof. Most preferred is when Eis selected from the group consisting of vinyl, allyl, acryloyl,methacryloyl, ethacryloyl, styryl, 3-vinylbenzyl, 4-vinylbenzyl, andmixtures thereof. In the above structure m is preferably an integer fromabout 10 to about 2000, more preferably from about 15 to about 300, andmost preferably from about 20 to about 250.

Alternatively, other examples of endcapped poly(N-alkyloxazoline)macromonomers are those having the following chemical formula:

wherein R and R′ are independently selected from the group consisting ofH or C₁₋₈ straight or branched chain alkyl, more preferably R and R′ areindependently selected from H, methyl, or ethyl; and most preferably Ris H and R′ is ethyl. In the above structure m is an integer from about10 to about 2000, more preferably from about 15 to about 300, and mostpreferably from about 20 to about 250.

Highly preferred examples of endcapped poly(N-alkyloxazoline)macromonomers useful herein include acryloyl endcapped poly(2-ethyloxazoline), methacryloyl endcapped poly(2-ethyl oxazoline), styrylendcapped poly(2-ethyloxazoline), acryloyl endcapped poly(2-methyloxazoline), methacryloyl endcapped poly(2-methyl oxazoline),3-vinylbenzoyl endcapped poly(2-methyloxazoline), 4-vinylbenzoylendcapped poly(2-methyloxazoline), and mixtures thereof.

The endcapped poly(N-alkyloxazoline) macromonomers can be synthesizedusing standard synthetic procedures which involve polymerizing, usuallyunder acid-catalyzed conditions, an N-alkyloxazoline to yield apoly(N-alkyloxazoline) alcohol. This alcohol can then be subsequentlyendcapped, employing standard reaction procedures, with the desiredethylenically unsaturated moiety using a reactive or activated form ofan endcapping group. Suitable activated endcapping groups include vinyl,allyl, 1-propenyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, and4-vinylbenzoyl halides (e.g. chlorides, bromides, and iodides), and theacid chlorides and bromides derived from acrylic acid, methacrylic acid,and ethacrylic acid. See, e.g., S. I. Shoda et al., “Synthesis andSurfactant Property of Copolymers Having a Poly(2-Oxazoline) GraftChain”, Journal of Polymer Science: Part A: Polymer Chemistry, vol. 30,pp. 1489-1494 (1992); T. Saegusa et al., “Macromolecular Engineering onthe Basis of the Polymerization of 2-Oxazolines, Makromol. Chem.,Macromol. Symp., vol. 51, pp. 1-10 (1991); S. Kobayashi et al.,Macromolecules, vol 22, pp. 2878-2884 (1989), and U.S. Pat. No.4,011,376, to Tomalia et al., issued Mar. 8, 1977; and U.S. Pat. No.3,186,116, to Milkovich et al., issued Jan. 15, 1974; all of which areincorporated herein by reference.

Alternatively the polyoxazoline macromonomers can be synthesized bypolymerizing the monomers onto an appropriate endcapping group. Forexample, the vinyl benzyl endcapped polyoxazolines can be prepared bypolymerizing 2-ethyl-2-oxazoline onto a mixture of 3-vinylbenzyl and4-benzylchlorides. See EXAMPLE III.

Also highly useful herein are endcapped polyalkylene glycolmacromonomers and polyalkylene glycol monoalkyl ether macromonomerscorresponding to the following chemical formula

wherein R″ is selected from hydrogen and C1-C40 straight or branchedchain alkyl, more preferably from hydrogen and C1-C8 straight orbranched chain alkyl, most preferably from hydrogen and C1-C4 straightor branched chain alkyl, and most preferably from hydrogen and methyl;R³ is selected from hydrogen, methyl, ethyl, or n-propyl, morepreferably from hydrogen or methyl, most preferably from H. E is acopolymerizable, ethylenically unsaturated moiety (i.e. the endcappingmoiety). Preferred is when E is selected from the group consisting ofvinyl, allyl, acryloyl, methacryloyl, ethacryloyl, styryl,3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl,1-propenyl, isobutenyl, isoprenyl, cyclohexyl, cylcopentyl, and mixturesthereof. More preferred is when E is selected from the group consistingof vinyl, allyl, acryloyl, methacryloyl, ethacryloyl, 3-vinylbenzyl,4-vinylbenzyl, 3-vinylbenzoyl, 4-vinylbenzoyl, 1-butenyl, 1-propenyl,isobutenyl, and mixtures thereof. Most preferred is when E is selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, styryl, 3-viinylbenzyl, 4-vinylbenzyl, and mixturesthereof. In the above structure, m is as described previously, wherein mis preferably an integer from about 20 to about 2000, more preferablyfrom about 30 to about 750, and most preferably from about 40 to about500. It is to be understood that in the above structure, that when R³ isother than hydrogen that various isomers of the resulting macromonomerare possible depending upon the orientation of the individual glycolmoieties. Therefore, the structure depicted above for these endcappedpolyalkylene glycol monolkayl ethers is a general one that is notintended to limit these materials to any one particular isomericstructure.

Highly preferred examples of endcapped polyalkylene glycol monoalkylethers useful herein inlcude acryloyl endcapped polyethylene glycol,3-vinylbenzoyl endcapped polyethylene glycol, 4-vinylbenzoyl endcappedpolyethylene glycol, methacryloyl endcapped polyethylene glycol,acryloyl endcapped polyethylene glycol monomethyl ether, 3-vinylbenzoylendcapped polyethylene glycol monomethyl ether, 4-vinylbenzoyl endcappedpolyethylene glycol monomethyl ether, methacryloyl endcappedpolyethylene glycol monomethyl ether, and mixtures thereof.

The endcapped polyalkylene glycols and their monoalkyl ethers can besynthesized from the polyalkylene glycol or its monoalkyl ether and thereactive or activated form of an endcapping group employing standardreaction procedures. Suitable activated endcapping groups include vinyl,allyl, 3-vinylbenzoyl, and 4-vinylbenzoyl halides (e.g. chlorides,bromides, and iodides), and the acid chlorides and bromides derived fromacrylic acid, methacrylic acid, and ethacrylic acid. The polyalkyleneglycol monoalkyl ether can be synthesized from the correspondingpolyalkylene glycol using any of the alkylating agents well known in theart (e.g., methyl iodide, methyl bromide, diazomethane, methyl sulfate,ethyl iodide). Polyethylene glycols of various molecular weight ranges,as well as their methyl ethers are commercially available from AldrichChemical Company and Union Carbide Corporation. Alternatively, thepolyalkylene glycols can be synthesized from the corresponding alkyleneoxides and alkylene glycols using standard synthetic procedures (e.g.,the acid or base catalyzed polymerization of alkylene oxides).

Polysiloxane C Macromonomer Units

The polysiloxane C macromonomer units are large monomer buIlding blockscontaining a polysiloxane portion (i.e. a polysiloxane chain) and amoiety copolymerizable with said A and B units. A polysiloxane is apolymer containing repeating silicon-oxygen bonds.

The polysiloxane C monomer units comprise from about 0.1% to about 20%,more preferably from about 1% to about 15%, and most preferably fromabout 2% to about 10%, by weight of the copolymers.

By the term “copolymerizable” as used herein is meant C polysiloxanemacromonomer units that can be reacted with the A monomer and the Bmacromonomer in a polymerization reaction using any conventionalsynthetic techniques. The C polysiloxane macromonomer units that areuseful herein contain a copolymerizable moiety, preferably anethylenically unsaturated moiety, that is copolymerizalbe with the A andB units. The term “ethylenically unsaturated” is used herein to mean Cpolysiloxane units that contain at least one carbon-carbon double bond(which can be mono-, di-, tri-, or tetra-substituted). Typically, thepreferred C polysiloxanes are those that are endcapped with theethylenically unsaturated moiety. By “endcapped” as used herein is meantthat the ethylenically unsaturated moiety is at or near a terminalposition of the macromonomer. However, this definition of “endcapped” isnot intended to limit the macromonomer to only those macromonomers whichterminate in a carbon-carbon double bond (whether mono-, di-, tri-, ortetra-substituted).

Examples of polysiloxane macromonomer units which are useful as thepolysiloxane C units herein are described in U.S. Pat. No. 5,106,609, toR. E. Bolich, Jr. et al., issued Apr. 21, 1992; and U.S. Pat. No.4,693,935, to Mazurek, issued Sep. 15, 1987, which are both incorporatedby reference herein in their entirety. Either a single C polysiloxanemacromonomer or combinations or two or more C polysiloxane macromonomerscan be utilized. In either case, the polysiloxane macromonomers areselected to meet the requirements of the copolymer.

The C polysiloxane units can be described by the following formula

E′(Y)_(n)Si(R⁷)_(3-t)(Z)_(t)

wherein E′ is an ethylenically unsaturated moiety or “endcapping” groupcopolymerizable with A and B; Y is a divalent linking atom or group ofatoms; R⁷ is selected from the group consisting of H, lower alkyl, aryl,or alkoxy; Z is a monovalent siloxane polymeric moiety having a numberaverage molecular weight of at least about 500, is essentiallyunreactive under copolymerization conditions, and is pendant from saidbackbone after polymerization; n is 0 or 1; and t is an integer from 1to 3.

The C unit has a weight average molecular weight of from about 1000 toabout 50,000, preferably from about 5000 to about 40,000, morepreferably from about 10,000 to about 20,000.

Preferred C polysiloxane units are those selected from the groupconsisting of

 E′—Si(R¹¹)_(3-t)Z_(t)

wherein t is 1, 2, or 3, preferably t is 1; p is 0 or 1, preferably p is0; R⁸ is alkyl or hydrogen; q is an integer from 2 to 6, preferably q is3; s is an integer from 0 to 2; E′ is represented by the structure

wherein R⁹ is hydrogen or —COOH, preferably R⁹ is hydrogen; R₁₀ ishydrogen, methyl or —CH₂COOH, preferably R¹⁰ is methyl; Z is

wherein R¹¹ is alkyl, alkoxy, alkylamino, aryl, or hydroxyl, preferablyR¹¹ is alkyl); and r is an integer from about 5 to about 700, preferablyr is about 250.

Polymers of the Present Invention

Particularly preferred polymers for use in the present invention includethe following (the weight percents below refer to the amount ofreactants added in the polymerization reaction, not necessarily theamount in the finished polymer):

n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazo-line)/poly(dimethylsiloxane) 36/22/40/2

n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazo-line)/poly(dimethylsiloxane) 33/22/40/5

n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazo-line)/poly(dimethylsiloxane)30.5/22/40/7.5

n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazo-line)/poly(dimethylsiloxane) 28/22/40/10

n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazo-line)/poly(dimethylsiloxane) 23/22/40/15

n-butyl acrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane)53/40/7

n-butyl acrylate/2-ethylhexylmethacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane) 35/20/40/5

n-butyl acrylate/2-methoxyethyl acrylate/poly(ethyleneglycol)/poly(dimethylslloxane) 36/22/40/2

n-butyl acrylate/2-(dimethylamino)ethylmethacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane) 31/24/40/5

n-butyl acrylate/methyl quaternized 2-(dimethylamino)ethylmethacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane) 31/24/40/5

Synthesis of the Copolymers

The copolymers can be made by free radical polymerization of the Amonomers with the B macromonomers and C polysiloxane macromonomers. Itis not intended to necessarily exclude from this invention anycopolymers made by means other than free radical polymerization, so longas the product has the desired physical properties. The copolymersherein are formed from randomly repeating A monomer units, Bmacromonomer units, and C polysiloxane macromonomer units.

The general principles of free radical polymerization methods are wellunderstood. See, for example, Odian, “Principles of Polymerization”, 2ndedition, John Wiley & Sons, 1981, pp. 179-318. The desired monomers andmacromonomers are all placed in a reactor, along with a sufficientamount of a mutual solvent so that when the reaction is complete theviscosity of the reaction is reasonable. Typical monomer andmacromonomer loadings are from about 10% to about 50%, on a weightbasis. Undesired terminators, especially oxygen, can be removed asneeded. This is done by evacuation or by purging with an inert gas, suchas argon or nitrogen. The initiator is introduced and the reactionbrought to the temperature needed for initiation to occur, assumingthermal initiators are used. Nonlimiting examples of suitable initiatorsinclude those selected from the group consisting of azo initiators,peroxide initiators, redox initiators, and photochemical initiators. Thepolymerization is allowed to proceed as long as needed for a high levelof conversion to be achieved, typically from a few hours to a few days.The solvent is then removed, usually by evaporation or by precipitatingthe copolymer by addition of a nonsolvent. The copolymer can be furtherpurified, as needed utilizing a variety of techniques includingfiltration, extraction, trituration, membrane separation, gel permeationchromatography, and like.

There are numerous variations on these procedures which are entirely upto the discretion of the synthetic chemist (e.g., choice of degassingmethod and gas, choice of initiator type, extent of conversion, reactionloading, etc). The choice of initiator and solvent are often determinedby the requirements of the particular monomers and macromonomer used,because different monomers and macromonomers have different solubilitiesand different reactivities to a specific initiator.

The copolymers of the present invention can also be synthesized by firstpreparing the backbone and polysiloxane side chains from thecopolymerization of suitable monomers and polysiloxane macromonomers,followed by further polymerization of the resulting intermediarycopolymer with suitable hydrophilic monomers to form the hydrophilicside chains. This alternative procedure for synthesizing the copolymersherein is illustrated in EXAMPLE VI below. In yet other alternatives,the polysiloxane side chains can be added by polymerizingsilicon-containing moieties onto an intermediate copolymer prepared fromsuitable macromonomers and hydrophilic macromonomers.

Analysis of the copolymer reaction product and the extracted materials,and the purified copolymer can be performed by conventional analysistechniques known in the art. These include, for example, nuclearmagnetic resource (NMR), infrared molecular spectroscopies, gelpermeation/size exclusion chromatography, membrane osmometry, and atomicabsorption and emission spectroscopies.

Hair Care and Topical Skin Care Compositions

The copolymers of the present invention can be formulated into a widevariety of product types, including mousses, gels, lotions, tonics,sprays, shampoos, conditioners, rinses, hand and body lotions, facialmoisturizers, sunscreens, anti-acne preparations, topical analgesics,mascaras, and the like. The carriers and additional components requiredto formulate such products vary with product type and can be routinelychosen by one skilled in the art. The following is a description of someof these carriers and additional components.

Carriers

Hair Care Compositions

The hair care compositions of the present invention can comprise acarrier, or a mixture of such carriers, which are suitable forapplication to the hair. The carriers are present at from about 0.5% toabout 99.5%, preferably from about 5.0% to about 99.5%, more preferablyfrom about 10.0% to about 98.0%, of the composition. As used herein, thephrase “suitable for application to hair” means that the carrier doesnot damage or negatively affect the aesthetics of hair or causeirritation to the underlying skin.

Carriers suitable for use with hair care compositions of the presentinvention include, for example, those used in the formulation of hairsprays, mousses, tonics, gels, shampoos, conditioners, and rinses. Thechoice of appropriate carrier will also depend on the particularcopolymer to be used, and whether the product formulated is meant to beleft on the surface to which it is applied (e.g., hair spray, mousse,tonic, or gel) or rinsed off after use (e.g., shampoo, conditioner,rinse).

The carriers used herein can include a wide range of componentsconventionally used in hair care compositions. The carriers can containa solvent to dissolve or disperse the particular copolymer being used,with water, the C1-C6 alcohols, and mixtures thereof being preferred;and water, methanol, ethanol, isopropanol, and mixtures thereof beingmore preferred. The carriers can also contain a wide variety ofadditional materials including, but not limited to acetone, hydrocarbons(such as isobutane, hexane, decene), halogenated hydrocarbons (such asFreons), linalool, esters (such as ethyl acetate, dibutyl phthalate),and volatile silicon derivatives (especially siloxanes such as phenylpentamethyl disiloxane, methoxypropyl heptamethyl cyclotetrasiloxane,chloropropyl pentamethyl disiloxane, hydroxypropyl pentamethyldisiloxane, octamethyl cyclotetrasiloxane, decamethylcyclopentasiloxane, cyclomethicone, and dimethicone having for example,a viscosity at 25° C. of about 15 centipoise or less), and mixturesthereof. When the hair care composition is a hair spray, tonic, gel, ormousse the preferred solvents include water, ethanol, volatile siliconederivatives, and mixtures thereof. The solvents used in such mixturesmay be miscible or immiscible with each other. Mousses and aerosol hairsprays can also utilize any of the conventional propellants to deliverthe material as a foam (in the case of a mousse) or as a fine, uniformspray (in the case of an aerosol hair spray). Examples of suitablepropellants include materials such as trichlorofluoromethane,dichlorodifluoromethane, difluoroethane, dimethylether, propane,n-butane or isobutane. A tonic or hair spray product having a lowviscosity may also utilize an emulsifying agent. Examples of suitableemulsifying agents include nonionic, cationic, anionic surfactants, ormixtures thereof. Fluorosurfactants are especially preferred,particularly if the product is a hair spray composition and mostespecially if it is a spray composition having relatively low levels ofvolatile organic solvents, such as alcohols, and relatively high levelsof water (e.g., in excess of about 10%, by weight water). If such anemulsifying agent is used, it is preferably present at a level of fromabout 0.01% to about 7.5% of the composition. The level of propellantcan be adjusted as desired but is generally from about 3% to about 30%of mousse compositions and from about 15% to about 50% of the aerosolhair spray compositions.

Suitable spray containers are well known in the art and includeconventional, non-aerosol pump sprays i.e., “atomizers,” aerosolcontainers or cans having propellant, as described above, and also pumpaerosol containers utilizing compressed air as the propellent. Pumpaerosol containers are disclosed, for example, in U.S. Pat. No.4,077,441, Marc. 7, 1978, Olofsson and U.S. Pat. No. 4,850,577, Jul. 25,1989, TerStege, both incorporated by reference herein, and also in U.S.Ser. No. 07/839,648, Gosselin, Lund, Sojka, and Lefebvre, filed Feb. 21,1992, “Consumer Product Package Incorporating A Spray Device UtilizingLarge Diameter Bubbles. Pump aerosols hair sprays using compressed airare also currently marketed by The Procter & Gamble Company under theirtradename VIDAL SASSOON AIRSPRAY® hair sprays.

Where the hair care compositions are conditioners and rinses the carriercan include a wide variety of conditioning materials. Where the haircare compositions are shampoos, the carrier can include surfactants,suspending agents, thickeners etc. Various additional components usefulin hair care compositions are described in U.S. Pat. No. 5,106,609, toBolich, Jr. et al., issued Apr. 21, 1992; and U.S. Pat. No. 4,387,090,to Bolich, Jr. issued Jun. 7, 1983; which are incorporated by referenceherein. Some of these additional components are described below.

Topical Skin Care Compositions

The topical cosmetic and pharmaceutical compositions of the presentinvention can comprise a carrier. The carrier should be “cosmeticallyand/or pharmaceutically acceptable”, which means that the carrier issuitable for topical application to the skin, has good aestheticproperties, is compatible with the copolymers of the present inventionand any other components, and will not cause any untoward safety ortoxicity concerns.

The carrier can be in a wide variety of forms. For example, emulsioncarriers, including, but not limited to, oil-in-water, water-in-oil,water-in-oil-in-water, and oil-in-water-in-silicone emulsions, areuseful herein. These emulsions can cover a broad range of viscosities,e.g, from about 100 cps to about 200,000 cps. These emulsions can alsobe delivered in the form of sprays using either mechanical pumpcontainers or pressurized aerosol containers using conventionalpropellants. These carriers can also be delivered in the form of amousse. Other suitable topical carriers include anhydrous liquidsolvents such as oils, alcohols, and silicones (e.g., mineral oil,ethanol, isopropanol, dimethicone, cyclomethicone, and the like);aqueous-based single phase liquid solvents (e.g., hydro-alcoholicsolvent systems); and thickened versions of these anhydrous andaqueous-based single phase solvents (e.g., where the viscosity of thesolvent has been increased to form a solid or semi-solid by the additionof appropriate gums, resins, waxes, polymers, salts, and the like).Examples of topical carrier systems useful in the present invention aredescribed in the following four references all of which are incorporatedherein by reference in their entirety: “Sun Products Formulary”Cosmetics & Toiletries, vol. 105, pp. 122-139 (December 1990); “SunProducts Formulary”, Cosmetics & Toiletries, vol. 102, pp. 117-136(March 1987); U.S. Pat. No. 4,960,764 to Figueroa et al., issued Oct. 2,1990; and U.S. Pat. No. 4,254,105 to Fukuda et al., issued Mar. 3, 1981.

The carriers of the skin care compositions can comprise from about 50%to about 99% by weight of the compositions of the present invention,preferably from about 75% to about 99%, and most preferably from about85% to about 95%.

Preferred cosmetically and/or pharmaceutically acceptable topicalcarriers include hydro-alcoholic systems and oil-in-water emulsions.When the carrier is a hydro-alcoholic system, the carrier can comprisefrom about 1% to about 99% of ethanol, isopropanol, or mixtures thereof,and from about 1% to about 99% of water. More preferred is a carriercomprising from about 5% to about 60% of ethanol, isopropanol, ormixtures thereof, and from about 40% to about 95% of water. Especiallypreferred is a carrier comprising from about 20% to about 50% ofethanol, isopropanol, or mixtures thereof, and from about 50% to about80% of water. When the carrier is an oil-in-water emulsion, the carriercan include any of the common excipient ingredients for preparing theseemulsions. Additional components useful in formulating these topicalcompositions are further described below.

Additional Components

A wide variety of additional components can be employed in the hair careand topical skin compositions herein. Non-limiting examples include thefollowing:

Pharmaceutical Actives

The compositions of the present invention, especially the topical skincare compositions, can comprise a safe and effective amount of apharmaceutical active. The phrase “safe and effective amount”, as usedherein, means an amount of an active high enough to significantly orpositively modify the condition to be treated, but low enough to avoidserious side effects (at a reasonable benefit/risk ratio), within thescope of sound medical judgement. A safe and effective amount of thepharmaceutical active will vary with the specific active, the ability ofthe composition to penetrate the active through the skin, the amount ofcomposition to be applied, the particular condition being treated, theage and physical condition of the patient being treated, the severity ofthe condition, the duration of the treatment, the nature of concurrenttherapy, and like factors.

The pharmaceutical actives which can be used in the compositions of thepresent invention preferably comprise from 10 about 0.1% to about 20% byweight of the compositions, more preferably from about 0.1% to about10%, and most preferably from about 0.1% to about 5%. Mixtures ofpharmaceutical actives may also be used.

Nonlimiting examples of pharmaceutical actives can include thefollowing:

Useful pharmaceutical actives in the compositions of the presentinvention include anti-acne drugs. Anti-acne drugs preferred for use inthe present invention include the keratolytics such as salicylic acid,sulfur, lactic acid, glycolic, pyruvic acid, urea, resorcinol, andN-acetylcystelne; retinoids such as retinoic acid and its derivatives(e.g., cis and trans); antibiotics and antimicrobials such as benzoylperoxide, octopirox, erythromycin, zinc, tetracyclin, triclosan, azelaicacid and its derivatives, phenoxy ethanol and phenoxy proponol,ethylacetate, clindamycin and meclocycline; sebostats such asflavinoids; alpha and beta hydroxy acids; and bile salts such as scymnolsulfate and its derivatives, deoxycholate, and cholate. Preferred foruse herein is salicylic acid.

Useful pharmacetuical actives in the compositions of the presentinvention include non-steroidal anti-inflammatory drugs (NSAIDS). TheNSAIDS can be selected from the following categories: propionic acidderivatives; acetic acid derivatives; fenamic acid derivatives;biphenylcarboxylic acid derivatives; and oxicams. All of these NSAIDSare fully described in the U.S. Pat. No. 4,985,459 to Sunshine et al.,issued Jan. 15, 1991, incorporated by reference herein. Most preferredare the propionic NSAIOS including but not limited to aspirin,acetaminophen, ibuprofen, naproxen, benoxaprofen, flurbiprofen,fenoprofen, fenbufen, ketoprofen, indoprofen, pirprofen, carprofen,oxaprozin, pranoprofen, miroprofen, tioxaprofen, suprofen, alminoprofen,tiaprofenic acid, fluprofen and bucloxic acid. Also useful are thesteroidal anti-inflammatory drugs including hydrocortisone and the like.

Useful pharmaceutical actives in the compositions of the presentinvention include antipruritic drugs. Antipruritic drugs preferred forinclusion in compositions of the present invention includepharmaceutically-acceptable salts of methdilizine and trimeprazine.

Useful pharmaceutical actives in the compositions of the presentinvention include include anesthetic drugs. Anesthetic drugs preferredfor inclusion in compositions of the present invention includepharmaceutically-acceptable salts of lidocaine, bupivacaine,chlorprocaine, dibucaine, etidocalne, mepivacaine, tetracaine,dyclonine, hexylcaine, procaine, cocaine, ketamine, pramoxine andphenol.

Useful pharmaceutical actives in the compositions of the presentinvention include antimicrobial drugs (antibacterial, antifungal,antiprotozoal and antiviral drugs). Antimicrobial drugs preferred forinclusion in compositions of the present invention includepharmaceutically-acceptable salts of β-lactam drugs, quinolone drugs,ciprofloxacin, norfloxacin, tetracycline, erythromycin, amikacin,triclosan, doxycycline, capreomycin, chlorhexidine, chlortetracycline,oxytetracycline, clindamycin, ethambutol, metronidazole, pentamidine,gentamicin, kanamycin, lineomycin, methacycline, methenamine,minocycline, neomycin, netilmicin, paromomycin, streptomycin,tobramycin, miconazole and amanfadine. Antimicrobial drugs preferred forinclusion in compositions of the present invention include tetracyclinehydrochloride, erythromycin estolate, erythromycin stearate (salt),amikacin sulfate, doxycycline hydrochloride, capreomycin sulfate,chlorhexidine gluconate, chlorhexidine hydrochloride, chlortetracyclinehydrochloride, oxytetracycline hydrochloride, clindamycin hydrochloride,ethambutol hydrochloride, metronidazole hydrochloride, pentamidinehydrochloride, gentamicin sulfate, kanamycin sulfate, lineomycinhydrochloride, methacycline hydrochloride, methenamine hippurate,methenamine mandelate, minocycline hydrochloride, neomycin sulfate,netilmicin sulfate, paromomycin sulfate, streptomycin sulfate,tobramycin sulfate, miconazole hydrochloride, amanfadine hydrochloride,amanfadine sulfate, triclosan, octopirox, parachlorometa xylenol,nystatin, tolnaftate and clotrimazole.

Also useful herein are sunscreening agents. A wide variety ofsunscreening agents are described in U.S. Pat. No. 5,087,445, to Haffeyet al., issued Feb. 11, 1992; U.S. Pat. No. 5,073,372, to Turner et al.,issued Dec. 17, 1991; U.S. Pat. No. 5,073,371, to Turner et al. issuedDec. 17, 1991; and Segarin, et al., at Chapter VIII, pages 189 et seq.,of Cosmetics Science and Technology, all of which are incorporatedherein by reference in their entirety.

Preferred among those sunscreens which are useful in the compositions ofthe instant invention are those selected from the group consisting of2-ethylhexyl p-methoxycinnamate, 2-ethylhexylN,N-dimethyl-p-aminobenzoate, p-aminobenzoic acid,2-phenylbenzimidazole-5-sulfonic acid, octocrylene, oxybenzone,homomenthyl salicylate, octyl salicylate,4,4′-methoxy-1-butyldibenzoylmethane, 4-isopropyl dibenzoylmethane,3-benzylidene camphor, 3-(4-methylbenzylidene) camphor, titaniumdioxide, zinc oxide, silica, iron oxide, and mixtures thereof.

Still other useful sunscreens are those disclosed in U.S. Pat. No.4,937,370, to Sabatelli, issued Jun. 26, 1990; and U.S. Pat. No.4,999,186, to Sabatelli et al., issued Mar. 12, 1991; these tworeferences are incorporated by reference herein in their entirety. Thesunscreening agents disclosed therein have, in a single molecule, twodistinct chromophore moieties which exhibit different ultra-violetradiation absorption spectra. One of the chromophore moieties absorbspredominantly in the UVB radiation range and the other absorbs stronglyin the UVA radiation range. These sunscreening agents provide higherefficacy, broader UV absorption, lower skin penetration and longerlasting efficacy relative to conventional sunscreens. Especiallypreferred examples of these sunscreens include those selected from thegroup consisting of 4-N,N-(2-ethylhexyl)methylaminobenzoic acid ester of2,4-dihydroxybenzophenone, 4-N,N-(2-ethylhexyl)methylaminobenzoic acidester with 4-hydroxydibenzoylmethane,4-N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of2-hydroxy-4-(2-hydroxyethoxy)benzophenone,4-N,N-(2-ethylhexyl)-methylaminobenzoic acid ester of4-(2-hydroxyethoxy)dibenzoylmethane, and mixtures thereof.

Generally, the sunscreens can comprise from about 0.5% to about 20% ofthe compositions useful herein. Exact amounts will vary depending uponthe sunscreen chosen and the desired Sun Protection Factor (SPF). SPF isa commonly used measure of photoprotection of a sunscreen againsterythema. See Federal Register, Vol. 43, No. 166, pp. 38206-38269, Aug.25, 1978, which is incorporated herein by reference in its entirety.

Also useful in the present invention are sunless tanning agentsincluding dihydroxyacetone, glyceraldehyde, indoles and theirderivatives, and the like. These sunless tanning agents may also be usedin combination with the sunscreen agents.

Other useful actives include skin bleaching (or lightening) agentsincluding but not limited to hydroquinone, ascorbic acid, kojic acid andsodium metabisulfite.

Other useful actives which are especially useful for hair carecompositions include anti-dandruff actives such as zinc pyrithione,octopirox, selenium disulfide, sulfur, coal tar, and the like.

Conditioners

Conditioning agents useful herein, and especially useful for hair carecompositions, include hydrocarbons, silicone fluids, and cationicmaterials.

The hydrocarbons can be either straight or branched chain and cancontain from about 10 to about 16, preferably from about 12 to about 16carbon atoms. Examples of suitable hydrocarbons are decane, dodecane,tetradecane, tridecane, and mixtures thereof.

Silicone conditioning agents useful herein can include either cyclic orlinear polydimethylsiloxanes, pheny and alkyl phenyl silicones, andsilicone copolyols. The linear volatile silicones generally haveviscosities of less than about 5 centistokes at 25° C., while the cylicmaterials have viscosities less than about 10 centistokes.

Cationic conditioning agents useful herein can include quaternaryammonium salts or the salts of fatty amines. Preferred quaternaryammonium salts are dialkyl dimethyl ammonium chlorides, wherein thealkyl groups have from 12 to 22 carbon atoms and are derived fromlong-chain fatty acids. Representative examples of quaternary ammoniumsalts include ditallow dimethyl ammonium chloride, ditallow dimethylammonium methyl sulfate, dihexadecyl dimethyl ammonium chloride, anddi(hydrogenated tallow) ammonium chloride. Other qauternary ammoniumsalts useful herein are dicatlonics such as tallow propane diammoniumdichloride. Quaternary imidazolinium salts are also useful herein.Examples of such materials are those imidazolinium salts containingC12-22 alkyl groups such as1-methyl-1-[(stearoylamide)ethyl]-2-heptadecyl-4, 5-dihydroimidazoliniumchloride,1-methyl-1-[(palmitoylamide)ethyl]-2-octadecyl-4,5-dihydroimidazoliniumchloride and 1-methyl-1-[(tallowamide)-ethyl]-2-tallow-imidazoliniummethyl sulfate. Also useful herein are salts of fatty amines. Examplesof such compounds include stearylamine hydrochloride, soyaminehydrochloride, and stearylamine formate. Useful conditioning agents aredisclosed in U.S. Pat. No. 4,387,090, to Bolich, issued Jun. 7, 1983,which is incorporated by reference herein.

Humectants and Moisturizers

The compositions of the present invention can contain one or morehumectant or moisturizing materials. A variety of these materials can beemployed and each can be present at a level of from about 0.1% to about20%, more preferably from about 1% to about 10% and most preferably fromabout 2% to about 5%. These materials include urea; guanidine; glycolicacid and glycolate salts (e.g. ammonium and quaternary alkyl ammonium);lactic acid and lactate salts (e.g. ammonium and quaternary alkylammonium); aloe vera in any of its variety of forms (e.g., aloe veragel); polyhydroxy alcohols such as sorbitol, glycerol, hexanetriol,propylene glycol, butylene glycol, hexylene glycol and the like;polyethylene glycols; sugars and starches; sugar and starch derivatives(e.g., alkoxylated glucose); hyaluronic acid; lactamidemonoethanolamine; acetamide monoethanolamine; and mixtures thereof.Preferred humectants and moisturizers are glycerol, butylene glycol,hexylene glycol, and mixtures thereof.

Surfactants

The compositions of the present invention, especially the shampoo andconditioner compositions, can contain one or more surfactants. Thesesurfactants are useful adjuncts for the carriers of the presentcompositions, and are not required for solubilizing or dispersing thecopolymers of the present invention. For a shampoo, the level ispreferably from about 10% to about 30%, preferably from 12% to about25%, of the composition. For conditioners, the preferred level ofsurfactant is from about 0.2% to about 3%. Surfactants useful incompositions of the present invention include anionic, nonionic,cationic, zwitterionic and amphoteric surfactants. A wide variety ofsurfactants useful herein are disclosed in U.S. Pat. No. 5,151,209, toMc Call et al., issued Sep. 29, 1992; U.S. Pat. No. 5,151,210, to Steuriet al., issued Sep. 29, 1992; and U.S. Pat. No. 5,120,532, to Wells etal., issued Jun. 9, 1992, all of which are incorporated by referenceherein.

Nonlimiting examples of these surfactants include anionic surfactantssuch as alkyl and alkyl ether sulfates. These materials typically havethe respective formulae ROSO₃N and RO(C₂H₄O)_(x)SO₃M, wherein R is alkylor alkenyl of from about 10 to about 20 carbon atoms, x is 1 to 10, andM is a water-soluble cation such as ammonium, sodium, potassium andtriethanolamine. Another suitable class of anionic surfactants are thewater-soluble salts of the organic, sulfuric acid reaction products ofthe formula:

R₁—SO₃—M

wherein R₁ is chosen from the group consisting of a straight or branchedchain, saturated aliphatic hydrocarbon radical having from about 8 toabout 24, preferably about 12 to about 18, carbon atoms; and M is acation. Additional examples of anionic synthetic surfactants which comewithin the terms of the present invention are the reaction products offatty acids esterified with isethionic acid and neutralized with sodiumhydroxide where, for example, the fatty acids are derived from coconutoil; sodium or be potassium salts of fatty acid amides of methyl tauridein which the fatty acids, for example, are derived from coconut oil.Still other anionic synthetic surfactants include the class designatedas succinamates, olefin sulfonates having about 12 to about 24 carbonatoms, and β-alkyloxy alkane sulfonates. Many additional nonsoapsynthetic anionic surfactants are described in McCutcheon's, Detergentsand Emulsifiers, 1984 Annual, published by Allured PublishingCorporation, which is incorporated herein by reference. Also U.S. Pat.No. 3,929,678, Laughlin et al., issued Dec. 30, 1975, discloses manyother anionic as well as other surfactant types and is incorporatedherein by reference.

Nonionic surfactants useful herein are preferably used in combinationwith an anionic, amphoteric or zwitterionic surfactant. These nonionicsurfactants can be broadly defined as compounds produced by thecondensation of alkylene oxide groups (hydrophilic in nature) with anorganic hydrophobic compound, which may be aliphatic or alkyl aromaticin nature.

Cationic surfactants useful in compositions of the present invention aredisclosed In the following documents, all incorporated by referenceherein: M.C. Publishing Co., McCutcheon's, Detergents & Emulsifiers,(North American edition 1979); Schwartz, et al., Surface Active Agents,Their Chemistry and Technology, New York: Interscience Publishers, 1949;U.S. Pat. No. 3,155,591, Hilfer, issued Nov. 3, 1964; U.S. Pat. No.3,929,678, Laughlin, et al., issued Dec. 30, 1975; U.S. Pat. No.3,959,461, Bailey, et al., issued May 25, 1976; and U.S. Pat. No.4,387,090, Bolich, Jr., issued Jun. 7, 1983. If included in thecompositions of the present invention, the cationic surfactant ispresent at from about 0.05% to about 5%.

Zwitterionic surfactants are exemplified by those which can be broadlydescribed as derivatives of aliphatic quaternary ammonium, phosphonium,and sulfonium compounds, in which the aliphatic radicals can be straightor branched chain, and wherein one of the aliphatic substituentscontains from about 8 to about 18 carbon atoms and one contains ananionic water-solubilizing group, e.g., carboxy, sulfonate, sulfate,phosphate, or phosphonate. Other zwitterionics such as betaines are alsouseful in the present invention. Examples of betaines include the highalkyl betaines, such as coco dimethyl carboxymethyl betaine, lauryldimethyl carboxymethyl betaine, lauryl dimethyl alpha-carboxyethylbetaine, cetyl dimethyl carboxymethyl betaine, laurylbis-(2-hydroxyethyl) carboxymethyl betaine, stearylbis-(2-hydroxypropyl) carboxymethyl betaine, oleyl dimethylgamma-carboxypropyl betaine, laurylbis-(2-hydroxypropyl)alpha-carboxyethyl betaine, coco dimethylsulfopropyl betaine, stearyl dimethyl sulfopropyl betaine, lauryldimethyl sulfoethyl betaine, lauryl bis-(2-hydroxyethyl) sulfopropylbetaine, and amidobetaines and amidosulfobetaines (wherein theRCONH(CH₂)₃ radical is attached to the nitrogen atom of the betaine).

Examples of amphoteric surfactants which can be used in the compositionsof the present invention are those which are broadly described asderivatives of aliphatic secondary and tertiary amines in which thealiphatic radical can be straight or branched chain and wherein one ofthe aliphatic substituents contains from about 8 to about 18 carbonatoms and one contains an anionic water solubilizing group, e.g.,carboxy, sulfonate, sulfate, phosphate, or phosphonate. Examples ofcompounds falling within this definition are sodium3-dodecyl-aminopropionate, sodium 3-dodecylaminopropane sulfonate,N-alkyltaurines such as the one prepared by reacting dodecylamine withsodium isethionate according to the teaching of U.S. Pat. No. 2,658,072,N-higher alkyl aspartic acids such as those produced according to theteaching of U.S. Pat. No. 2,438,091, and the products sold under thetrade name “Miranol” and described in U.S. Pat. No. 2,528,378.

Carboxylic Acid Copolymer Thickeners

Another component useful in the compositions herein is a carboxyliccopolymer thickener. These crosslinked polymers contain one or moremonomers derived from acrylic acid, substituted acrylic acids, and saltsand esters of these acrylic acids and the substituted acrylic acids,wherein the crosslinking agent contains two or more carbon-carbon doublebonds and is derived from a polyhydric alcohol. The preferred polymersfor use herein are of two general types. The first type of polymer is acrosslinked homopolymer of an acrylic acid monomer or derivative thereof(e.g., wherein the acrylic acid has substituents on the two and threecarbon positions independently selected from the group consisting ofC₁₋₄ alkyl, —CN, —COOH, and mixtures thereof). The second type ofpolymer is a crosslinked copolymer having a first monomer selected fromthe group consisting of an acrylic acid monomer or derivative thereof(as just described in the previous sentence), a short chain alcohol(i.e. a C₁₋₄) acrylate ester monomer or derivative thereof (e.g.,wherein the acrylic acid portion of the ester has substituents on thetwo and three carbon positions independently selected from the groupconsisting of C₁₋₄ alkyl, —CN, —COOH, and mixtures thereof), andmixtures thereof; and a second monomer which is a long chain alcohol(i.e. C₈₋₄₀) acrylate ester monomer or derivative thereof (e.g., whereinthe acrylic acid portion of the ester has substituents on the two andthree carbon positions independently selected from the group consistingof C₁₋₄ alkyl, —CN, —COOH, and mixtures thereof). Combinations of thesetwo types of polymers are also useful herein.

In the first type of crosslinked homopolymers the monomers arepreferably selected from the group consisting of acrylic acid,methacrylic acid, ethacrylic acid, and mixtures thereof, with acrylicacid being most preferred. In the second type of crosslinked copolymersthe acrylic acid monomer or derivative thereof is preferably selectedfrom the group consisting of acrylic acid, methacrylic acid, ethacrylicacid, and mixtures thereof, with acrylic acid, methacrylic acid, andmixtures thereof being most preferred. The short chain alcohol acrylateester monomer or derivative thereof is preferably selected from thegroup consisting of C₁₋₄ alcohol acrylate esters, C₁₋₄ alcoholmethacrylate esters, C₁₋₄ alcohol ethacrylate esters, and mixturesthereof, with the C₁₋₄ alcohol acrylate esters, C₁₋₄ alcoholmethacrylate esters, and mixtures thereof, being most preferred. Thelong chain alcohol acrylate ester monomer is selected from C₈₋₄₀ alkylacrylate esters, with C₁₀₋₃₀ alkyl acrylate esters being preferred.

The crosslinking agent in both of these types of polymers is apolyalkenyl polyether of a polyhydric alcohol containing more than onealkenyl ether group per molecule, wherein the parent polyhydric alcoholcontains at least 3 carbon atoms and at least 3 hydroxyl groups.Preferred crosslinkers are those selected from the group consisting ofallyl ethers of sucrose and allyl ethers of pentaerythritol, andmixtures thereof. These polymers useful in the present invention aremore fully described in U.S. Pat. No. 5,087,445, to Haffey et al.,issued Feb. 11, 1992; U.S. Pat. No. 4,509,949, to Huang et al., issuedApr. 5, 1985; U.S. Pat. No. 2,798,053, to Brown, issued Jul. 2, 1957;which are incorporated by reference herein. See also, CTFA InternationalCosmetic Ingredient Dictionary, fourth edition, 1991, pp. 12 and80;which are also incorporated herein by reference.

Examples of commercially available hompolymers of the first type usefulherein include the carbomers, which are homopolymers of acrylic acidcrosslinked with allyl ethers of sucrose or pentaerytritol. Thecarbomers are available as the Carbopol^(R) 900 series from B.F.Goodrich. Examples of commercially available copolymers of the secondtype useful herein include copolymers of C₁₀₋₃₀ alkyl acrylates with oneor more monomers of acrylic acid, methacrylic acid, or one of theirshort chain (i.e. C₁₋₄ alcohol) esters, wherein the crosslinking agentis an allyl ether of sucrose or pentaerytritol. These copolymers areknown as acrylates/C₁₀₋₃₀ alkyl acrylate crosspolymers and arecommercially available as Carbopol^(R) 1342, Pemulen TR-1, and PemulenTR-2, from B.F. Goodrich. In other words, examples of carboxylic acidpolymer thickeners useful herein are those selected from the groupconsisting of carbomers, acrylates/C10-C30 alkyl acrylate crosspolymers,and mixtures thereof.

The compositions of the present can comprise from about 0.025% to about1%, more preferably from about 0.05% to about 0.75% and most preferablyfrom about 0.10% to about 0.50% of the carboxylic acid polymerthickeners.

Emulsifiers

The compositions herein can contain various emulsifiers. Theseemulsifiers are useful for emulsifying the various carrier components ofthe compositions herein, and are not required for solubilizing ordispersing the copolymers of the present Invention. Suitable emulsifierscan include any of a wide variety of nonionic, cationic, anionic, andzwitterionic emulsifiers disclosed in the prior patents and otherreferences. See McCutcheon's, Detergents and Emulsifiers, North AmericanEdition (1986), published by Allured Publishing Corporation; U.S. Pat.No. 5,011,681 to Ciotti et al., issued Apr. 30, 1991; U.S. Pat. No.4,421,769 to Dixon et al., issued Dec. 20, 1983; and U.S. Pat. No.3,755,560 to Dickert et al., issued Aug. 28, 1973; these four referencesare incorporated herein by reference in their entirety.

Suitable emulsifier types include esters of glycerin, esters ofpropylene glycol, fatty acid esters of polyethylene glycol, fatty acidesters of polypropylene glycol, esters of sorbitol, esters of sorbitananhydrides, carboxylic acid copolymers, esters and ethers of glucose,ethoxylated ethers, ethoxylated alcohols, alkyl phosphates,polyoxyethylene fatty ether phosphates, fatty acid amides, acyllactylates, soaps and mixtures thereof.

Suitable emulsifiers can include, but are not limited to, polyethyleneglycol 20 sorbitan monolaurate (Polysorbate 20), polyethylene glycol 5soya sterol, Steareth-20, Ceteareth-20, PPG-2 methyl glucose etherdistearate, Ceteth-10, Polysorbate 80, cetyl phosphate, potassium cetylphosphate, diethanolamine cetyl phosphate, Polysorbate 60, glycerylstearate, PEG-100 stearate, and mixtures thereof.

The emulsifiers can be used individually or as a mixture of two or moreand can comprise from about 0.1% to about 10%, more preferably fromabout 1% to about 7%, and most preferably from about 1% to about 5% ofthe compositions of the present invention.

Emollients

The compositions useful in the methods of the present invention can alsooptionally comprise at least one emollient. Examples of suitableemollients include, but are not limited to, volatile and non-volatilesilicone oils, highly branched hydrocarbons, and non-polar carboxylicacid and alcohol esters, and mixtures thereof. Emollients useful in theinstant invention are further described in U.S. Pat. No. 4,919,934, toDeckner et al., issued Apr. 24, 1990, which is incorporated herein byreference in its entirety.

The emollients can typically comprise in total from about 1% to about50%, preferably from about 1% to about 25%, and more preferably fromabout 1% to about 10% by weight of the compositions useful in thepresent invention.

Additional Components

A variety of additional components can be incorporated into thecompositions herein. Non-limiting examples of these additionalcomponents include vitamins and derivatives thereof (e.g., ascorbicacid, vitamin E, tocopheryl acetate, retinoic acid, retinol, retinoids,and the like); low pH thickening agents (e.g. polyacrylamide and C₁₃₋₁₄isoparaffin and laureth-7, available as Sepigel from Seppic Corporation;polyquaternium and mineral oil, available as Salcare SC92, from AlliedCollolds; crosslinked methyl quaternized dimethylaminomethacrylate andmineral oil, available as Salcare SC95 from Allied Colloids; resins;gums and thickeners such as xanthan gum, carboxymethyl cellulose,hydroxymethyl cellulose, hydroxyethyl cellulose, alkyl-modifiedhydroxyalkyl celluloses (e.g. long chain alkyl modified hydroxyethylcelluloses such as cetyl hydroxyethylcellulose), and magnesium aluminumsilicate; cationic polymers and thickeners (e.g., cationic guar gumderivatives such as guar hydroxypropyltrimonium chloride andhydroxypropyl guar hydroxypropyltrlmonium chloride, available as theJaguar C series from Rhone-Poulenc; polymers for aiding the film-formingproperties and substantivity of the composition (such as a copolymer ofeicosene and vinyl pyrrolidone, an example of which is available fromGAF Chemical Corporation as Ganex^(R) V-220); suspending agents such asethylene glycol distearate and the like; preservatives for maintainingthe antimicrobial integrity of the compositions; skin penetration aidssuch as DMSO, 1-dodecylazacycloheptan-2-one (available as Azone from theUpjohn Co.) and the like; antioxidants; chelators and sequestrants; andaesthetic components such as fragrances, colorings, essential oils, skinsensates, astringents, skin soothing agents, skin healing agents and thelike, nonlimiting examples of these aesthetic components includepanthenol and derivatives (e.g. ethyl panthenol), pantothenic acid andits derivatives, clove oil, menthol, camphor, eucalyptus oil, eugenol,menthyl lactate, witch hazel distillate, allantoin, bisabalol,dipotassium glycyrrhizinate and the like.

Method of Using Hair and Skin Care Compositions

The hair care and skin care compositions of the present invention areused in conventional ways to provide the desired benefit appropriate tothe product such as hair styling, holding, cleansing, conditioning andthe like for hair care compositions and benefits such as moisturization,sun protection, anti-acne, anti-wrinkling, artificial tanning,analgesic, and other cosmetic and pharmaceutical benefits for skin carecompositions. Such methods of use depend upon the type of compositionemployed but generally involve application of an effective amount of theproduct to the hair or skin, which may then be rinsed from the hair orskin (as in the case of shampoos and some conditioning products) orallowed to remain on the hair (as in the case of spray, mousse, or gelproducts), or allowed to remain on the skin lie=(as in the case of theskin care compositions). By “effective amount” is meant an amountsufficient to provide the benefit desired. Preferably, hair rinse,mousse, and gel products are applied to wet or damp hair prior to dryingand styling of the hair. After such compositions are applied to thehair, the hair is dried and styled in the usual ways of the user. Hairsprays are typically applied to dry hair after it has already been driedand styled. Cosmetic and pharmaceutical topical skin care compositionsare applied to and rubbed into the skin.

The following examples further illustrate preferred embodiments withinthe scope of the present invention. The examples are given solely forthe purposes of illustration and are not to be construed as limitationsof the present invention as many variations of the invention arepossible without departing from its spirit and scope.

EXAMPLES

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The examples are given solelyfor the purpose of illustration and are not to be construed aslimitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.

Ingredients are identified by chemical or CTFA name.

Example I Synthesis of Poly(2-ethyl-2-oxazoline) Alcohol

To a solution of 50 g (0.5044 mol) of 2-ethyl-2-oxazoline in 50 mL ofacetonitrile is added 0.92 g (0.0048 mol) of methyl-p-toluenesulfonateat 0° C. under a nitrogen atmosphere. The reaction mixture is heated at80° C. for 20 hours and the resulting polymer solution is then refluxedwith 2.3 mL distilled water in the presence of 5.6 g (0.0528 mol) ofsodium carbonate for 24 hours. The solvents are removed under vacuum.The residue is extracted with 300 mL of dichloromethane for 24 hours,and the insolubles are removed by suction filtration. Thedichloromethane is then evaporated to yield about 48 g (96% yield) ofpoly(2-ethyl-2-oxazoline) alcohol.

Example II Synthesis of Acrylate-Capped Poly(2-ethyl-2-oxazoline)Macromonomer

To a solution of 48 g of poly(2-ethyl-2-oxazoline) alcohol (from EXAMPLEI) and 1.0 g (0.01056 mol) of triethylamine in 80 mL of dichloromethaneis added dropwise a solution of 0.95 g (0.01056 mol) of acryloylchloride at 0° C. under a nitrogen atmosphere. The reaction mixture isthen stirred at room temperature for 36 hrs, and the resulting solutionis then suction filtered to remove the insolubles. The solvent and anyunreacted triethylamine are removed by evaporation under vacuum. Theresulting solid is then redissolved in 200 mL of dichloromethane,filtered, and evaporated under vacuum to yield about 45.6 g (95% yield)of the macromonomer.

Using an analogous procedure the methacrylate and ethacrylate endcappedmacromonomers are prepared by replacing the acryloyl chloride with anequivalent molar amount of methacryloyl chloride and ethacryloylchloride, respectively.

Example III Synthesis of Vinylbenzyl-Capped Poly(2-ethyl-2-oxazoline)Macromonomer

To a solution of 50 g (0.5044 mol) of 2-ethyl-2-oxazoline in 50 mL ofacetonitrile is added a mixture of 0.3816 g (0.0025 mol) of meta andparavinylbenzylchlorides (available from Aldrich Chemical Co.), 0.562 g(0.0037 mol) of sodium iodide and 0.06 g (0.00023 mol) ofN,N′-diphenyl-p-phenylenediamine. The solution is then heated at 90° C.for 16 hours. To the resulting reaction product is added 100 mL ofdichloromethane and the solution is filtered and then precipitated in800 mL of ether. The precipitate product is collected by vacuumfiltration and dried under vacuum at ambient temperature to yield about45 g (90% yield) of the macromonomer.

Example IV Synthesis of Acrylate-Capped Poly(ethylene glycol)methylEther Macromonomer

To a solution of 50 g (0.01 mol) of poly(ethylene glycol)methyl etherhaving an average molecular weight of about 5000 (commercially availablefrom Aldrich Chemical Co.) and 4.05 g (0.04 mol) of triethylamine in 400mL of dichloromethane is added dropwise at 0° C. under a nitrogenatmosphere a solution of 2.26 g (0.025 mol) of acryloyl chloridedissolved in 25 mL of dichloromethane. The reaction mixture is thenstirred at room temperature for 36 hrs, and the resulting solution isthen suction filtered to remove the insolubles. The solvent and anyunreacted triethylamine are removed by evaporation under vacuum. Theresulting solid is then redissolved in 300 mL of dichloromethane,filtered, and evaporated under vacuum to yield about 50 g (100% yield)of the macromonomer.

The above procedure is varied using other poly(ethylene glycol)alkylethers (e.g. ethyl, propyl, 2-ethylhexyl, decyl, dodecyl, cetyl,stearyl, lauryl, and myristyl wherein the polymer has an averagemolecular weight varying from about 1000 to about 200,000) to obtain theanalogous acrylate-capped macromonomers. Additionally, the methacrylateand ethacrylate endcapped macromonomers are prepared by replacing theacryloyl chloride with an equivalent molar amount of methacryloylchloride and ethacryloyl chloride, respectively.

Example V Synthesis of Poly(n-butyl Acrylate-co-2-methoxyethylacrylate)-graft-[poly(2-ethyl-2-oxazoline); Poly(dimethylsiloxane)]Method 1

This polymer can be designated as having the following weightpercentages of monomers: n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane)

36/22/40/2

To a solution of 3.60 g (0.0281 mol) of n-butyl acrylate, 2.20 g (0.0169mol) of 2-methoxyethyl acrylate, 0.2 g (0.00002 mol)poly(diemthylsioxane) macromonomer (10,000 MW, commercially availablefrom Chisso Corp.; Tokyo, Japan) and 4.0 g (0.001 mol)poly(2-ethyl-2-oxazoline) macromonomer (from Example II) in 90 mL ofacetone is added 0.015 g (0.0001 mol) of azoisobutyronitrile (AIBN)initiator. The resulting solution is refluxed for about 24 hours. Thereaction is then quenched by the addition of about 5 mL of methanol. Thesolution is then poured into a teflon pan and the acetone is evaporatedat room temperature under a fume hood. The resulting polymer film isredissovled in ethanol, filtered, and the ethanol is then evaporated toyield about 9.0 g of the thermoplastic elastomeric copolymer.

Alternatively, 4.0 g of macromonomer from Example III is used to preparethe polymer.

Example VI Synthesis of Poly(n-butyl Acrylate-co-2-methoxyethylacrylate)-graft-[poly(2-ethyl-2-oxazoline); Poly(dimethylsiloxane)];Method 2

This polymer can be designated as having the following weightpercentages of monomers: n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane)

36/22/40/2

To a 250 mL round-bottomed flask is added 3.60 g (0.0281 mol) of n-butylacrylate, 2.20 g (0.0169 mol) of 2-methoxyethyl acrylate, 0.05 g (0.0003mol) 2-vinylbenzyl chloride, 0.20 g (0.0002 mol) poly(diemthylsioxane)macromonomer (10,000 MW, commercially available from Chisso Corp.;Tokyo, Japan), 0.015 g (0.0001 mol) azoisobutyronitrile (AIBN) initator,in 100 mL of acetone. The resulting solution is refluxed slowly forabout 24 hours. The reaction is then quenched by the addition of about 5mL of methanol and cooled to room temperature. The solvents are removedby rotary evaporation and the resulting polymer is dissolved in 100 mLof dry acetonitrile. Next 4.0 g (0.0403 mol) of 2-ethyl-2-oxazoline and0.90 g (0.0006 mol) of sodium iodide is added and the solution is heatedto 90° C. for 20 hours. The resulting solution is filtered and thesolvent is evaporated to yield about 8.0 g of the thermoplasticelastomeric copolymer.

Example VII Synthesis of Poly(n-butyl Acrylate-co-2-methoxyethylacrylate)-graft-[poly(2-ethyl-2-oxazoline); Poly(dimethylslloxane)]

This polymer can be designated as having the following weightpercentages of monomers: n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane)

33/22/40/5

This copolymer is made using the procedure in EXAMPLE V using thefollowing levels of ingredients: 3.60 g (0.0257 mol) of n-butylacrylate, 2.20 g (0.0169 mol) of 2-methoxyethyl acrylate, 0.5 g (0.00005mol) poly(diemthylsioxane) macromonomer (10,000 MW, commerciallyavailable from Chisso Corp.; Tokyo, Japan), 4.0 g (0.001 mol)poly(2-ethyl-2-oxazoline) macromonomer (from Example II), and 0.05 g(0.0003 mol) of azoisobutyronitrile (AIBN) initiator. About 9.0 g of thethermoplastic elastomeric copolymer is obtained.

Alternatively, 4.0 g of macromonomer from Example III is used to preparethe polymer.

Example VIII Synthesis of Poly(n-butyl Acrylate-co-2-methoxyethylAcrylate)-graft-[poly(2-ethyl-2-oxazoline); Poly(dimethylsiloxane)]

This polymer can be designated as having the following weightpercentages of monomers: n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane)

30.5/22/40/7.5

This copolymer is made using the procedure in EXAMPLE V using thefollowing levels of ingredients: 3.05 g (0.0238 mol) of n-butylacrylate, 2.20 g (0.0169 mol) of 2-methoxyethyl acrylate, 7.5 g (0.00075mol) poly(diemthylsioxane) macromonomer (10,000 MW, commerciallyavailable from Chisso Corp.; Tokyo, Japan), 4.0 g (0.001 mol)poly(2-ethyl-2-oxazoline) macromonomer (from Example II), and 0.03 g(0.0002 mol) of azoisobutyronitrile (AIBN) initiator. About 9.0 g of thethermoplastic elastomeric copolymer is obtained.

Alternatively, 4.0 g of macromonomer from Example III is used to preparethe polymer.

Example IX Synthesis of Poly(n-butyl Acrylate-co-2-methoxyethylAcrylate)-graft-[poly(2-ethyl-2-oxazoline); Poly(dimethylsiloxane)]

This polymer can be designated as having the following weightpercentages of monomers: n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane)

28/22/40/10

This copolymer is made using the procedure in EXAMPLE V using thefollowing levels of ingredients: 2.80 g (0.0218 mol) of n-butylacrylate, 2.20 g (0.0169 mol) of 2-methoxyethyl acrylate, 1.0 g (0.0001mol) poly(diemthylsioxane) macromonomer (10,000 MW, commerciallyavailable from Chisso Corp.; Tokyo, Japan), 4.0 g (0.001 mol)poly(2-ethyl-2-oxazoline) macromonomer (from Example II), and 0.05 g(0.0003 mol) of azoisobutyronitrile (AIBN) initiator. About 9.0 g of thethermoplastic elastomeric copolymer is obtained.

Alternatively, 4.0 g of macromonomer from Example III is used to preparethe polymer.

Example X Synthesis of Poly(n-butyl Acrylate-co-2-methoxyethylAcrylate)-graft-[poly(2-ethyl-2-oxazoline); Poly(dimethylsiloxane)]

This polymer can be designated as having the following weightpercentages of monomers: n-butyl acrylate/2-methoxyethylacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane)

23/22/40/15

This copolymer is made using the procedure in EXAMPLE V using thefollowing levels of ingredients: 2.30 g (0.0179 mol) of n-butylacrylate, 2.20 g (0.0169 mol) of 2-methoxyethyl acrylate, 1.5 g (0.00015mol) poly(diemthylsioxane) macromonomer (10,000 MW, commerciallyavailable from Chisso Corp.; Tokyo, Japan), 4.0 g(0.001 mol)poly(2-ethyl-2-oxazoline) macromonomer (from Example II), and 0.03 g(0.0002 mol) of azoisobutyronitrile (AIBN) initiator.

Alternatively, 4.0 g of macromonomer from Example III is used to preparethe polymer.

Example XI Synthesis of Poly(n-butylAcrylate)-graft-[poly(2-ethyl-2-oxazoline); Poly(dimethylsiloxane)]

This polymer can be designated as having the following weightpercentages of monomers: n-butylacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane)

53/40/7

This copolymer is made using the procedure in EXAMPLE V using thefollowing levels of ingredients: 10.60 g (0.0827 mol) of n-butylacrylate, 1.4 g (0.00014 mol) poly(diemthylsioxane) macromonomer (10,000MW, commercially available from Chisso Corp.; Tokyo, Japan), 8.0 g(0.002 mol) poly(2-ethyl-2-oxazoline) macromonomer (from Example II),and 0.03 g (0.0002 mol) of azoisobutyronitrile (AIBN) initiator, and 120mL of acetone. About 18.5 g of the thermoplastic elastomeric copolymeris obtained.

Alternatively, 8.0 g of macromonomer from Example III is used to preparethe polymer.

Example XII Synthesis of Poly(n-butyl Acrylate-co-2-ethylhexylMethacrylate)-graft-[poly(2-ethyl-2-oxazoline); Poly(dimethylsiloxane)]

This polymer can be designated as having the following weightpercentages of monomers: n-butyl acrylate/2-ethylhexylmethacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane) 35/20/40/5

This copolymer is made using the procedure in EXAMPLE V using thefollowing levels of ingredients: 3.50 g (0.0273 mol) of n-butylacrylate, 2.0 g (0.0101 mol) of 2-ethylhexyl methacrylate, 0.5 g(0.00005 mol) poly(dimethylsiloxane) macromonomer (10,000 MW,commercially available from Chisso Corp.; Tokyo, Japan), 4.0 g(0.001mol) poly(2-ethyl-2-oxazoline) macromonomer (from Example II), and 0.03g (0.0002 mol) of azoisobutyronitrile (AIBN) initiator, and 90 mL ofacetone. About 8.0 g of the thermoplastic elastomeric copolymer isobtained.

Alternatively, 4.0 g of macromonomer from Example III is used to preparethe polymer.

Example XIII Synthesis of Poly(n-butyl Acrylate-co-2-methoxyethylacrylate)-graft-[poly(ethylene glycol); Poly(dimethylsiloxane)]

This polymer can be designated as having the following weightpercentages of monomers: n-butyl acrylate/2-methoxyethylacrylate/poly(ethylene glycol)/poly(dimethylsiloxane)

36/22/40/2

To a solution of 3.60 g (0.0281 mol) of n-butyl acrylate, 2.20 g (0.0169mol) of 2-methoxyethyl acrylate, 0.2 g (0.00002 mol)poly(dimethylsiloxane) macromonomer (10,000 MW, commercially availablefrom Chisso Corp.; Tokyo, Japan) and 4.0 g poly(ethylene glycol)macromonomer (from Example IV) in 90 mL of acetone is added 0.015 g(0.0001 mol) of azoisobutyronitrile (AIBN) initiator. The resultingsolution is refluxed for about 24 hours. The reaction is then quenchedby the addition of about 5 mL of methanol. The solution is then pouredinto a teflon pan and the acetone is evaporated at room temperatureunder a fume hood. The resulting polymer film is redissovled in ethanol,filtered, and the ethanol is then evaporated to yield the thermoplasticelastomeric copolymer.

Example XIV Synthesis of Poly(n-butyl-co-2-(dimethylamino)ethylMethacrylate)-graft-[poly(2-ethyl-2-oxazoline); Poly(dimethylsiloxane)]Thermoplastic Elastomeric

This polymer can be designated as having the following weightpercentages of monomers: n-butyl acrylate/2-(dimethylamino)ethylmethacrylate/poly(2-ethyl-2-oxazoline)/poly(dimethylsiloxane)

31/24/40/5

To a solution of6.2 g (0.0484 mol) of n-butyl acrylate, 4.8 g (0.0305mol) of 2-(dimethylamino)ethyl methacrylate, and 8.0 gpoly(2-ethyl-2-oxazoline) macromonomer (from Example II), 1.0 g (0.0001mol) of poly(dimethylsioxane) macromonomer (10,000 MW, commerciallyavailable from Chisso Corp.; Tokyo, Japan) silicone MW 10,000 in 80 mLof acetone is added 0.01 g of AIBN initator. The resulting solution isrefluxed slowly for about 24 hours. The reaction is then quenched by theaddition of about 5 mL of methanol. The solution is then poured into ateflon pan and the acetone is evaporated at room temperature under afume hood. The resulting polymer film is redissovled in ethanol,filtered, and the ethanol is then evaporated to yield the thermoplasticelastomeric copolymer.

Alternatively, 8.0 g of macromonomer from Example III is used to preparethe polymer.

Example XV Synthesis of Methyl QuaternizedPoly(n-butyl-co-2-(dimethylamino)-ethylMethacrylate)-graft-[poly(2-ethyl-2-oxazoline); Poly(dimethylsiloxane)]Thermoplastic Elastomeric Copolymer

To 5 grams of the copolymer from EXAMPLE XIV dissolved in 80 grams ofethanol is added dropwise 2.16 g (0.0140 mole) of dimethylsulfate. Theresulting solution is stirred for 2 hours at room temperature. Thesolvent is removed by rotary evorpation to yield the methyl quaternizedcopolymer.

Example XVI Hair Spray

Hair spray compositions are prepared from the following componentsutilizing conventional mixing techniques.

Weight % Ingredients A B C D Water QS 100 QS 100 QS 100 QS 100 Ethanol(SDA 40) 79.0 79.0 79.0 90.0 Copolymer of Example V¹ 4.0 4.0 3.0 3.0Fragrance 0.1 0.2 — —

¹ Alternatively, spray compositions are prepared using the copolymers ofExamples VI, VII, VIII, IX, X, XIII, and XIV.

These products are prepared by first dissolving the polymer in theethanol with stirring. The water and fragrance are then added withstirring. The resulting hair spray compositions can then be packaged ina nonaerosol spray pump. Alternatively, the compositions can be combinedwith conventional propellants and packaged in an aerosol spray.

These hair sprays are useful for application to the hair to provide astyling and holding benefit.

Example XVII Reduced Volatile Organic Content Hairspray

Hair spray compositions are prepared from the following componentsutilizing conventional mixing techniques.

Weight % Ingredients A B C D Water QS 100 QS 100 QS 100 QS 100 Ethanol(SDA 40) 54.0 54.0 54.0 54.0 Copolymer of Example V¹ 4.0 3.0 4.0 3.0Fragrance 0.05 0.2 — —

¹ Alternatively, spray compositions are prepared using the copolymers ofExamples VI, VII, VIII, IX, X, XIII, and XIV.

These products are prepared by first dissolving the polymer in theethanol with stirring. The water and fragrance are then added withstirring. The resulting hair spray compositions can then be packaged ina nonaerosol spray pump. Alternatively, the compositions can be combinedwith conventional propellants and packaged in an aerosol spray.

These hair sprays are useful for application to the hair to provide astyling and holding benefit.

Example XVIII Mousse

Mousse compositions are prepared from the following components utilizingconventional mixing techniques.

Weight % Ingredients A B C Water QS 100 QS 100 QS 100 Copolymer ofExample XIV¹ 3.00 2.50 3.50 Lauramide DEA 0.33 0.33 0.33 Sodium MethylOleyl Taurate 1.67 1.67 1.67 DMDM Hydantoin 0.78 0.78 0.78 Disodium EDTA0.20 0.20 0.20 Polyoxyalkylated isostearyl 0.10 0.10 0.10 Alcohol²Fragrance 0.10 0.10 0.10 Propellant³ 7.0 7.0 7.0

¹ Alternatively, mousse compositions are prepared using the copolymer ofExample XV.

²Available as Aerosurf 66-E10.

³Available as a mixture of 82.46% isobutane, 16.57% propane, and 0.001%butane.

These products are prepared by first dissolving the polymer in waterwith stirring. The remaining ingredients, except the propellant, arethen added with stirring.

The resulting mousse concentrate can then be combined with conventionalpropellants (e.g., Propellant A46) and packaged in an aerosol spray.

These mousses are useful for application to the hair to provide astyling and holding benefit.

Example XIX Hair Tonic

Hair tonic compositions are prepared from the following componentsutilizing conventional mixing techniques.

Weight % Ingredients A B C Ethanol (SDA 40) QS 100 QS 100 QS 100Copolymer of Example V¹ 0.75 1.00 1.25 Fragrance 0.10 0.20 0.30

¹ Alternatively, tonic compositions are prepared using the copolymers ofExamples VI, VII, VIII, IX, X, XIII, and XIV.

These products are prepared by dissolving the polymer in the ethanolwith stirring and then adding the fragrance and any colors.

These hair tonics are useful for application to the hair to provide astyling and holding benefit.

Example XX Hair Conditioner

A hair conditioner composition is prepared from the following componentsutilizing conventional mixing techniques.

Weight % Ingredient A B Styling Agent Premix Copolymer of Example XV1.00 1.00 Silicone Premix Silicone gum, GE SE76¹ 0.30 0.30 Octamethylcyclotetrasiloxane 1.70 1.70 Main Mix Water QS100 QS100 Cetyl Alcohol1.00 — Quaternium 18² 0.85 0.85 Stearyl Alcohol 0.70 — HydroxethylCellulose 0.50 — Cetyl Hydroxyethyl Cellulose³ — 1.25 Ceteareth-20 0.35— Fragrance 0.20 0.20 Dimethicone copolyol 0.20 — Citric Acid 0.13 0.13Methylchloroisothiazolinone (and) 0.04 0.04 methylisothiazolinone SodiumChloride 0.01 0.01 Xanthan Gum — 0.20

¹ Commercially available from General Electric.

² Dimethyl Di(Hydrogenated Tallow) Ammonium Chloride

³ Commercially available as Polysurf D-67 from Aqualon.

The product is prepared by comixing all the Main Mix ingredients,heating to about 60° C. with mixing. The mixture is cooled to about 450Cwith colloid milling (Example A) or mixing (Example B). At thistemperature, the two premixes are add separately with moderate agitationand the resulting conditioner is allowed to cool to room temperature.

This product is useful as a rinse off hair conditioner.

Example XXI Shampoo Composition

A shampoo composition is prepared from the following componentsutilizing conventional mixing techniques.

Ingredients Weight % Styling Agent Copolymer from Example XV 1.00 PremixSilicone gum 0.50 Dimethicone, 350 cs fluid 0.50 Main Mix Water QS100Ammonium lauryl sulfate 11.00 Cocamide MEA 2.00 Ethylene glycoldistearate 1.00 Xanthan Gum 1.20 Methylchloroisothiazolinone (and) 0.04methylisothiazolinone Citric Acid to pH 4.5 as needed

The Main Mix is prepared by first dissolving the xanthan gum in thewater with conventional mixing. The remaining Main Mix ingredients areadded and the Main Mix is heated to 150° F. with agitation for ½ hour.The Styling Agent and the Premix are then added sequentially with about10 minutes of agitation between additions, and the entire mixture isstirred while the batch is cooled to room temperature. For variedparticile size, the Styling AGent and Premix can be added at differenttimes using either or both high shear mixing (high speed dispersator) ornormal agitation.

This shampoos is useful for cleansing the hear and for providing astyling benefit.

Example XXII Anti-Acne Composition

An anti-acne composition is made by combining the following componentsusing conventional mixing technology.

Ingredient Weight % Water QS100 Salicylic Acid 2.0 Copolymer fromExample V¹ 2.0 Ethanol (SDA 40) 40.0

¹ Alternatively, the anti-acne compositions are prepared using thecopolymers of Examples VI, VII, VIII, XIV, and XV.

The compositon display skin penetration of the salicylic acid as well asimproved skin reel and residue characteristics and is useful for thetreatment of acne.

Example XXIII Topical Analgesic Composition

A topical analgesic composition is made by combining the followingingredients utilizing conventional mixing techniques.

Ingredient Weight % Water, Purified QS100 Ibuprofen 2.0 Copolymer fromExample V¹ 2.0 Ethanol (SDA 40) 20.0

¹ Alternatively, the topical analagesic compositions are prepared usingthe copolymers of Examples VI, VII, XIII, XIV, and XV.

The compositions display skin penetration of the ibuprofen active aswell as improved skin feel and residue characteristics together withexcellent moisturizing, emolliency, rub-in and absorptioncharacteristics.

Example XXIV Sunless Tanning Composition

A composition for sunless tanning is made by combining the followingingredients utilizing conventional mixing techniques.

Ingredients Weight % Phase A Water qs 100 Copolymer from Example V¹ 2.00Carbomer 934² 0.20 Carbomer 980³ 0.15 Acrylic Acid Copolymer⁴ 0.15 PhaseB PPG-20 Methyl Glucose Ether 2.00 Distearate Tocopheryl Acetate 1.20Mineral Oil 2.00 Stearyl Alcohol 1.00 Shea Butter 1.00 Cetyl Alcohol1.00 Ceteareth-20 2.50 Ceteth-2 1.00 Ceteth-10 1.00 Phase C DEA-CetylPhosphate 0.75 Phase D Dihydroxyacetone 3.00 Phase E Butylene Glycol2.00 DMDM Hydantoin (and) 0.25 Iodopropynyl Butylcarbamate Phase FFragrance 1.00 Cyclomethicone 2.00

¹ Alternatively, the artificial tanning compositions are prepared usingthe copolymers of Examples VI, VII, XIII, XIV, XV.

² Available as Carbopol^(R) 934 from B.F. Goodrich.

³ Available as Carbopol^(R) 980 from B.F. Goodrich.

⁴ Available as Pemulen TR1 from B.F. Goodrich.

In a suitable vessel the Phase A ingredients are dispersed in the waterand heated to 75-85° C. In a separate vessel the Phase B ingredients arecombined and heated to 85-90° C. until melted. Next, the DEA-CetylPhosphate is added to the liquid Phase 8 and stirred until dissolved.This mixture is then added to Phase A to form the emulsion. The emulsionis cooled to 40-45° C. with continued mixing. Next, in a separatevessel, the dihydroxyacetone is dissolved in water and the resultingsolution is mixed into the emulsion. In another vessel, the Phase Eingredients are heated with mixing to 40-45° C. until a clear solutionis formed and this solution is then added to the emulsion. Finally, thePhase F ingredients are added to the emulsion with mixing, which is thencooled to 30-35° C., and then to room temperature.

This emulsion is useful for topical application to the skin to providean artificial tan.

Example XXV Sunscreen Composition

An oil-in-water emulsion is prepared by combining the followingcomponents utilizing conventional mixing techniques.

Ingredients Weight % Phase A Water QS100 Carbomer 954¹ 0.24 Carbomer1342² 0.16 Copolymer from Exmaple V³ 1.75 Disodium EDTA 0.05 Phase BIsoarachidyl Neopentanoate⁴ 2.00 PVP Eicosene Copolymer⁵ 2.00 OctylMethoxycinnamate 7.50 Octocrylene 4.00 Oxybenzone 1.00 Titanium Dioxide2.00 Cetyl Palmitate 0.75 Stearoxytrimethylsilane 0.50 (and) StearylAlcohol⁶ Glyceryl Tribehenate⁷ 0.75 Dimethicone 1.00 Tocopheryl Acetate0.10 DEA-Cetyl Phosphate 0.20 Phase C Water 2.00 Triethanolamine 99%0.60 Phase D Water 2.00 Butylene Glycol 2.00 DMDM Hydantoin (and) 0.25Iodopropynyl Butylcarbamate⁸ dL Panthenol 1.00 Phase E Cyclomethicone1.00 ¹ Available as Carbopol^(R) 954 from B.F. Goodrich. ² Available asCarbopol^(R) 1342 from B.F. Goodrich. ³ Alternatively, the sunscreencompositions are prepared using the copolymers of Examples VI, VII,XIII, XIV, and XV. ⁴ Available as Elefac I-205 from Bernel Chemical. ⁵Available as Ganex V-220 from GAF Corporation. ⁶ Available as DC 580 Waxfrom Dow Corning. ⁷ Available as Synchrowax HRC from Croda. ⁸ Availableas Glydant Plus from Lonza.

In a suitable vessel the Phase A ingredients are dispersed in the waterand heated to 75-85° C. In a separate vessel the Phase B ingredients(except DEA-Cetyl Phosphate) are combined and heated to 85-90° C. untilmelted. Next, the DEA-Cetyl Phosphate is added to the liquid Phase B andstirred until dissolved. This mixture is then added to Phase A to formthe emulsion. The Phase C ingredients are combined until dissolved andthen added to the emulsion. The emulsion is then cooled to 40-45° C.with continued mixing. In another vessel, the Phase D ingredients areheated with mixing to 40-45° C. until a clear solution is formed andthis solution is then added to the emulsion. Finally, the emulsion iscooled to 35° C. and the Phase E ingredient is added and mixed.

This emulsion is useful for topical application to the skin to provideprotection from the harmful effects of ultraviolet radiation.

Example XXVI Facial Moisturizer

A leave-on facial emulsion composition containing a cationic hydrophobicsurfactant is prepared by combining the following components utilizingconventional mixing techniques.

Ingredient Weight % Water QS100 Copolymer from Example V¹ 1.00 Glycerin3.00 Cetyl Palmitate 3.00 Cetyl Alcohol 1.26 Quaternium-22 1.00 GlycerylMonohydroxy Stearate 0.74 Dimethicone 0.60 Stearic Acid 0.55Octyldodecyl Myristate 0.30 Potassium Hydroxide 0.20 Carbomer 1342 0.125Tetrasodium EDTA 0.10 DMDM Hydantoin and Iodopropynyl 0.10 ButylCarbamate Carbomer 951 0.075

¹ Alternatively, the moisturizers are prepared using the copolymers ofExamples VI, VII, XIII, XIV, and XV.

This emulsion is useful for application to the skin as a moisturizer.

What is claimed is:
 1. A water or alcohol soluble or dispersiblethermoplastic elastomeric copolymer having a backbone and two or morehydrophilic polymeric side chains and one or more polysiloxane sidechains, said copolymer formed from the copolymerization of randomlyrepeating A, B, and C units wherein said copolymer comprises: (i) fromabout 20% to about 89.9% by weight of said A units, wherein said A unitsare monomer units that are copolymerizable with said B and C units; (ii)from about 10% to about 60% by weight of said B units, wherein said Bunits are hydrophilic macromonomer units having a polymeric portion anda moiety that is copolymerizable with said A and C units; and (iii) fromabout 0.1% to about 20% by weight of said C units, wherein said C unitsare polysiloxane macromonomer units having a polymeric portion and amoiety that is copolymerizable with said A and B units, wherein said Aunits, in conjunction with said copolymerizable moieties of said B unitsand said C units, form said backbone; wherein said polymeric portion ofsaid B units forms said hydrophilic side chains; wherein said polymericportion of said C units forms said polysiloxane side chains; whereinsaid copolymer has a weight average molecular weight greater than about10,000, and wherein said as copolymer exhibits at least two distinctT_(g) values, said first T_(g) corresponding to said backbone and havinga value less than about 0° C., and said second T_(g) corresponding tosaid hydrophilic polymeric side chains and having a value greater thanabout 25° C.
 2. A copolymer according to claim 1 wherein said A monomerunits are ethylenically unsaturated monomer units, said B macromonomerunits are units having a polymeric portion and an ethylenicallyunsaturated moiety that is copolymerizble with said A and C units, saidC macromonomer units are units having a polymeric portion and anethylenically unsaturated moiety that is copolymerizable with said A andB units, and said copolymer has a weight average molecular weight fromabout 10,000 to about 5,000,000.
 3. A copolymer according to claim 2wherein the T_(g) corresponding to said backbone is from about −45° C.to about −120° C., and the T_(g) corresponding to said hydrophilicpolymeric side chains is from about 35° C. to about 150° C.
 4. Acopolymer according to claim 3 wherein said A monomer units comprisefrom about 35% to about 85% by weight of the total copolymer, said Bmacromonomer units comprise from about 20% to about 55% by weight of thetotal copolymer, and said C polysiloxane macromonomer units comprisefrom about 1% to about 15% by weight of the total copolymer.
 5. Acopolymer according to claim 3 wherein said A monomer units comprisefrom about 50% to about 80% by weight of the total copolymer, said, Bmacromonomer units comprise from about 30% to about 50% by weight of thetotal copolymer, and said C polysiloxane macromonomer units comprisefrom about 2% to about 10% by weight of the total copolymer.
 6. Acopolymer according to claim 5 wherein said A monomer units are selectedfrom the group consisting of n-butyl acrylate, 2-ethylhexyl acrylate,N-octyl acrylamide, 2-methoxyethyl acrylate, 2-hydroxyethyl acrylate,N,N-dimethylaminoethyl acrylate, methyl quaternizedN,N-dimethylaminoethyl acrylate, and mixtures thereof.
 7. A copolymeraccording to claim 6 wherein said B macromonomer units are of theformula: [I]_(n′)—[W]_(m)—E wherein W is a hydrophilic monomer unitselected from the group consisting of oxazolines, N-alkyloxazolines,alkylene glycols, N-vinylpyrrolidones, N-allylpyrrolidones,vinylpyridines, allylpyridines, vinylcaprolactams, allylcaprolactams,vinylimidazoles, allylimidazoles, vinylfurans, allylfurans,vinyltetrahydrofurans, allyltetrahydrofurans, and mixtures thereof; m isan integer from about 10 to about 2000; E is a an ethylenicallyunsaturated endcapping moiety, copolymerizable with A and C, selectedfrom the group consisting of vinyl, allyl, acryloyl, methacryloyl,ethacryloyl, 3-vinylbenzyl, 4-vinylbenzyl, 3-vinylbenzoyl,4-vinylbenzoyl, and mixtures thereof; I is a chemical moiety derivedfrom an initiator selected from the group consisting of cationicinitiators and anionic initiators; and n is an integer selected from 0and
 1. 8. A copolymer according to claim 7 wherein said chemical moietyI is selected from the group consisting of H, hydroxy, methyl, ethyl,methoxy, ethoxy, and mixtures thereof.
 9. A copolymer according to claim8 wherein said polysiloxane macromonomer is of the formulaE′(Y)_(n)Si(R⁷)_(3-t)(Z)_(t) wherein E′ is an ethylenically unsaturatedmoiety copolymerizble with A and B; Y is a divalent linking group; R⁷ isselected from the group consisting of H, lower alkyl, aryl, or alkoxy; Zis a monovalent siloxane polymeric moiety having a number averagemolecular weight of at least about 500, is essentially unreactive undercopolymerization conditions, and is pendant from said backbone afterpolymerization; n is 0 or 1; and t is an integer from 1 to
 3. 10. Acopolymer according to claim 9 wherein said polysiloxane macromonomer isselected from the group consisting of

 E′—Si(R¹¹)_(3-t)Z_(t)

wherein t is 1, 2, or 3; p is 0 or 1; R⁸ is alkyl or hydrogen; q is aninteger from 2 to 6, s is an integer from 0 to 2; E′ is

wherein R⁹ is hydrogen or —COOH; R₁₀ is hydrogen, methyl or —CH₂COOH; Zis

R¹¹ is alkyl, alkoxy, alkylamino, aryl, or hdryoxyl; and r is an integerfrom about 5 to about 700.